key: cord-334329-puwf6ab5 authors: Yongjun, Gao; Liu, Jingbo; Bashir, Sajid title: Electrocatalysts for direct methanol fuel cells to demonstrate China's renewable energy renewable portfolio standards within the framework of the 13th five-year plan date: 2020-10-17 journal: Catal Today DOI: 10.1016/j.cattod.2020.10.004 sha: doc_id: 334329 cord_uid: puwf6ab5 A unified treatment of the renewable portfolio standards is given concerning direct methanol fuel. The current mechanism of electrocatalysis of methanol oxidation on platinum and non-platinum-containing alloys is summarized for the systematic improvement of the rate of electro-oxidation of methanol are discussed. Policy realignment under the five-year plan is discussed in length to demonstrate how policy, markets, and engineering designs contribute towards the development of model direct methanol fuel cells operational enhancement, and factors that affect critical performance parameters for commercial exploitation are summarized for catalytic formulations and cell design within the context of why this investment in technology, education, and finances is required within the global context of sustainable energy and energy independence as exposed by thirteenth the five-year plan. The prolog focuses on the way, whereas the section on methanol fuel cells on the how and the post log on what is expected post-COVID-19 era in science and technology as China pivots to a post-fossil fuel economy. China's industrial growth has been through internal market reforms and supplies side economics from the Chinese markets for fossil fuels except for petroleum. The latest renewable portfolio standards adopted have common elements as adopted from North American and the United Kingdom in terms of adaptation of obligation in terms of renewable portfolio standards as well as a realization that the necessity for renewables standards for the thirteen five year plan (from 2016 to 2020) need to less rigorously implemented due to performance targets that were met during the eleventh (06–10) and twelfth five-year plans (11–15) in terms of utilization of small coal-ire power plants, development of newer standards, led to an improvement of energy efficiency of 15 %, reduction of SO(x)/NO(x) by an average of 90 % and PM2.5 by 96 % over the last two five-year plans. The current phase of the plan has a focus on energy generation from coal and a slowing down of renewables or Renewable energy curtailment of approximately 400 T Wh renewables including 300 T Wh of non-hydro power, principally from Guangdong, and Jiangsu for transfer of hydropower and Zhejiang, Tianjin, Henan for non-hydro power transfer with Beijing and Shanghai playing important roles in renewables energy curtailment and realignment using an integrated approach to optimize each provinces energy portfolio. The realignment of the renewable energy portfolio indicates that the newly installed capacity in Sichuan, Yunnan, Inner Mongolia, and Zhejiang will account for less than 20 % of the current renewable energy portfolio but with the NO(x) SO(x) and PM(2.5) savings already accrued. The catalytic reduction of carbon dioxide to methanol (70 / 110 million metric tons from all sources in 2019 for China/world) is one technological approach to reduce global carbon dioxide emissions and suggests that catalytic methanol synthesis by CO(2) hydrogenation may be a plausible approach, even if it is more expensive economically than methanol synthesis by the syngas approach. This is because the CO(2) emissions of the synthesis are lower than other synthesis methodologies. The Chinese government has placed a premium on cleaner air and water and may view such an approach as solving the dual issues of fuel substitution and reduction of CO(2). Thus, the coupling of hydrogen generation from sustainable energies sources (Solar 175 / 509 GW) or wind (211/591.5 GW in 2019) may be an attractive approach, as this requires slightly less water than coal gasification. Due to the thermodynamic requirement of lower operating pressure and higher operating pressure, currently, there is no single operational approach, although some practice approaches (220 °C at 48 atm using copper) and zinc oxide/alumina are suggested for optimal performance. The chief aim of the State Council through the issuance of the five-year plans was to meet 'current challenges (Weng, 1983) , from positioning the republic to be a regional counterweight to Soviet Russia (Malenbaum, 1983) to an international global economic superpower (Wang, 2019a) can be seen through measurement of certain key performance indicators, chiefly amongst them was power generation (Yuan and Zuo, 2011) , as it was recognized early on that independence from outside agencies necessitated sufficient industrial, mechanization which in al. 2019a). The advantage of the proscribed approach is that it enables the grid utilities to integrate the renewable energy consumption obligation as part of the marketization process, where energy needs are met via a mix of renewable energy sources (Shi, 2018) . The utilities can also act as a coordinator with local consumers and power exchange centers for on-time transfer of electricity derived from renewable energy sources (Wang et al. 2019b ). The above investment plan is based on the State Council assessment that, the population and economic conditions of various regions on the Chinese mainland in 2019 show that the Chinese economy is still in a sound financial position with project growth (Vu, 2020) . The Table 1A . Although a generalization, the population of china is steady at around 1.4 billion which requires food and energy. The energy in terms of electricity and as liquid fuel for cars. This has resulted in large increases of carbon dioxide (CO2), particulate matter (PM), and sulfur oxides (SOx) being released into the environment. One solution is to convert CO2 directly to methanol and use methanol as a fuel in methanol fuel cells, as a blend with gasoline or as a precursor to generating other synthetic materials utilizing CO2 and H2. The case for which this should be considered will briefly be made, followed by a policy rationale of current and future policies as they're elated to energy and the environment and we will conclude with an extensive analysis of methanol hydrogenation and the catalyst and technologies utilized. According to the above figure, the economic growth rate in various regions of China is maintained at 3-8.1%, the strategic emerging industries are maintained at 2.3-14.9 %, and the natural population growth rate is between -1.8 and 12.3 ‰. The growth rate and range span not only show that China's energy problems cannot be viewed centrally but at the provincial level (Zhu, Fan, Shi, and Shi, 2019; Li, Hong, and Peng, 2019b; Shan, et al. 2019) . This suggests the methanol-based economy might assist China will the twin goals of energy independence and the lowering of carbon dioxide emissions. Global production of methanol is around 140 million tones (55 Billion USD) of which China contributes approximately 51%. China also consumes approximately 55 % of the world methanol, therefore imports methanol. Of the entire continuum of methanol consumed approximately 40 % chemicals & fuels; 20.5 % in dimethyl ether (DME) fuels; and 37.5% for traditional precursors. in 2020, it was estimated that approximately 61.5% of chemicals & fuels; 16.5 % in DME fuels; and 20.5% for traditional precursors (Zangeneh, Sahebdelfar, and Ravanchi, 2011) . Most of the methanol to olefins (MTO) , and methanol to propylene (MTP), methanol to gasoline (MTG), Methanol to aromatics (MTA), Ethylene glycol (EG) with three or more plants in Inner Mongolia, Henan, Shaanxi, and Shandong. methanol can be synthesized from biomass, natural gas, coal, or ta sand, via synthesis gas. Syngas is often produced through the gasification of biomass, by catalytic reforming of the feedstock biomass to synthetic gas and then catalytic synthesis of methanol from the synthesis gas (Surisetty, Dalai, and Kozinski, 2011) . With fossil fuels, this can be accomplished by steam reforming, oxy reforming, or CO2 reforming steps. In the first step that is auto thermal in nature, the endothermic steam reforming process and exothermic oxy reforming step are coupled to generate methanol. Methanol (physical properties summarized in Table 1B ) can also be generated by direct oxidation of methane, using catalytic gas-phase or liquid-phase oxidations or conversion of mono halogenated methane to methanol or using bioreactors with enzymes. Our favored approach is the chemical recycling of CO2 to methanol (He, Sun, and Han, 2013) . As stated, earlier methanol can be used directly to generate electricity via direct methanol fuel cells. The fuel cells have electrodes, an electrolyte, and a membrane from which protons can migrate. The methanol feed is at the anode, whilst oxygen is taken at the cathode with platinum (cathode), platinum ungsten-based (anode) catalyst (Eqn: 1 and figure 2B ). The anode can abstract a proton from methanol. When operated between 60-130 C enough electricity is generated to power storage batteries or small appliances. Oxidation of carbon J o u r n a l P r e -p r o o f dioxide to methanol is energetically unfavorable, as carbon has a formal oxidation charge of C 4+ to CH3OH, with a formal change of C 2-, therefore requiring six electrons, requiring 228 kJ/mol. For photooxidation, the metal oxide bandgap (~3.2 eV) to the reduction potential of CO2 would be required (Linsebigler, Lu, and Yates Jr, 1995) . Figure 2B : A schematic of a direct methanol fuel cell Anode: CH3OH + H2  CO2 + 6H + + 6e (1a) Cathode: 1.5 O2 + 6H + +6e  3H2O (1b) Overall Reaction: CH3OH + 1.5 O2  CO2 + 2H2O (1c) Methanol can also be blended into gasoline to increase the octane number of gasoline and increase the energy efficiency of the internal combustion engine. or directly as a methanol fuel cell in fuel cell cars or methanol powered vehicles and even as a fuel for heating. Methanol to gasoline (MTG) or methanol to olefins (MTO) to produce plastics is another application. Lastly, methanol can be used to produce biodiesel via transesterification of vegetable oil or as a marine fuel. J o u r n a l P r e -p r o o f The tables above shown that methanol has a higher energy density than methanol, is safer to transport than ethanol and gasoline, although itself is a potential poison. The hydrogenation of CO2 to methanol will be discussed in the concluding section. The current state of the economy within the framework of the current five-year plan will be described. J o u r n a l P r e -p r o o f Based on the geographical location, climatic conditions, agricultural and industrial foundation, population distribution, and other factors, the development of the various provinces in the mainland has shifted from a managed command economy to the present more decentralized approach (Wu, Zuidema, and Gugerell, 2018) . Particularly during the development leading up to and beyond the Beijing Olympics industrial technology and energy development has geared up to the utility of renewable energy at the level of the province away from petrochemical coal and petroleum to non-hydro renewables (Cherni, and Kentish, 2007) . China's northwest region is famous for its abundant coal, wind, light, and oil and gas resources. The southwest region is characterized by abundant water resources and other renewable energy resources (Di Silvestre, Favuzza, Sanseverino, and Zizzo, 2018) . The coastal areas are represented by nuclear energy and wind power (Qin, Liu, Li, and Li, 2017) . The State Council has directed each province to meet the renewable energy portfolio obligation via a multimodal complementarity approach coordinated with regional energy providers. Here, harmonized regional development is placed in the context of green energy obligations, where energy input and greenhouse gases and particulate matter as outputs development, are managed, which are currently implemented by regions in Anhui, Henan, Hubei, and Shanxi which has led to a reduction of carbon dioxide relative to the 2018 benchmark shown in figure 3A for 2018 and 2010 in figure 3B (Kozyrev, 2016; Chen, Zhou, and Yang, 2017) . J o u r n a l P r e -p r o o f Based on the statistical analysis from the NBSC the reform related to the reduction of electricity price and the consumption of clean energy have not been met (Fang, et al. 2019 (Yang, Chen, Zhou, and Ren, 2018) . Seven provinces continued to emphasize energy reform, increase the consumption of renewable energy, optimize the energy structure, and adjust the proportion of clean energy mix, and seven regions focused on natural gas, summarized in Table 2A . J o u r n a l P r e -p r o o f At present, every province in China needs to meet the expectations, but the mechanism can be different from each other (Yang, Hu, Tan, and Li, 2016) . First, continue to diversify the energy mix with a focus on renewable energy sources. The second distributed energy both temporarily and spatially. Third, coordinated energy production and usage with enough overcapacity (Dong, et al. 2019) . When comparing energy production and consumption at the provincial level through assessment of SOx, NOx, and CO2, some generalization can be stated starting from the 11 th five -year plan to the thirteenth five-year plan, summarized in figure 4 (Hu, 2016) . The progressive decreases of NOx and SOx during the 1990-2000 decade, increased in the early 2000s due to increased electricity generation and industrial production and infrastructure (Qin et al. 2018; . These increases in emission were related to the Beijing Olympics, cement production peak in April and October of 2005 of a modal value of 8.5 thousand tons of cement, with production declining from Jan-April (Lei, Zhang, Nielsen, and He, 2011) . Cement production then increased back to 10 thousand tons and crept up to about 22 thousand tons per year by and stayed constant except for a slight increase in 2014 (Gao, et al. 2017 ) and a slight decrease in 2020 due to a slowdown in the Chinese economy due to the coronavirus ). J o u r n a l P r e -p r o o f Streets, and Waldhoff, 2000a; Streets, Tsai, Akimoto, and Oka, 2000b; Shi, et al. 2014 . Note 1 mole C/liter = 12.011 × 10 -3 Gt C/km 3 , (using an atmospheric volume of 5.639  10 18 km 3 using an atmospheric mass of 5.137 × 10 18 kg and an air density of 0.911 kg/km 3 ), we calculate that 1 gigaton of C is equivalent to 0.470 ppm of C, or 1 ppm is equivalent to 2.;13 gigaton of carbon which is consistent with published data. A similar calculation for Sulfur (yields 1 gigaton to 0.176 ppm) and Nitrogen (1 gigaton to 0.403 ppm). The data from various sources was fin different units and was converted to ppm. In this manner, some artifacts were introduced, and some areas may be overestimated or underestimated in the graph should be viewed as a trend rather than specific end-point values). Most of the emissions were from the generation of electricity from fossil fuel consumption, but emissions from heavy industries including the production of cement cannot be ignored (Cai, et al. 2008) . In general CO2 emissions increased from west to east and north to south. Most reduction over the five-year plan (11 th to 12 th ) decreased by 15.8 % which is on target, with the greatest reductions occurring in Xinjiang, Shaanxi, Guangxi, Guangdong, and Fujian, with J o u r n a l P r e -p r o o f current reductions occurring in the South and Northwest provinces (Tollefson, 2016) . The provinces have to balance its balance to generate a gross domestic product to that of transitioning to low-carbon sources for energy, such as Beijing, Shanghai, and Guangdong focus will be on efficiency enhancements and development of solar, whereas Shanxi, Inner Mongolia, Xinjiang, Ningxia, and Guizhou focus will be on carbon capture due to an abundance of fossil resources (Zhu, et al. 2020) . Since the gross domestic product (GDP) and economic resources of central and western provinces in China are lower, utilization of low carbon energy sources or carbon capture may be more appropriate pathways towards increasing both GDP and lowering CO2 emissions (Zhang, and Hao, 2015) . Recently, the central government issued a consultative document entitled "Opinions on accelerating the establishment of a green production and consumption regulatory and policy system through the national development and reform commission and the ministry of justice" on March 17, 2020. The opinion if promogulated will be administered by the ministry of justice, strengthening law-based energy governance (Shen, Li, Wang, and Liao, 2020) . The core purpose of the opinions is to promote clean energy development, increase policy support for distributed energy, smart power grid, energy storage technology, and multi-energy complementarity, and research and formulate standards, regulations, and support policies for the development of new energy sources such as hydrogen energy and marine energy ). The energy balance should incorporate the whole life cycle, via the industrial chain to evaluate whether the energy supply and consumption meet the requirements of green and clean development. This may be promoted by recent rises in the particulate matter which were stable with a slight increase in 2005 and then a large rise in 2015 (Yue, et al. 2020 ). In China's "Completed of the thirteenth five-year plan and opening of the fourteenth five- year plan" period, we can see clearly that the Chinese government is promoting "the coordinated development of Beijing-Tianjin-Hebei region", (Lei, et al. 2020ab ) "the Yangtze River economic belt", , "Yangtze river delta integration development", "Guangdong-Hong Kong-Macao Greater Bay Area" (Bai, and Li, 2020a) and "the Belt and Road" (Winter, 2020 ) new five regional development strategy, further formed the new pattern of linkage with whole areas, overall planning for regional and marine economic activities and coordinated development (Xu, et al. 2020) . It shows that China's new space J o u r n a l P r e -p r o o f geographic economic phenomenon more and more clear, enters the new coordinated development stage of regional economic coordination and ecological environmental governance, comprehensive energy-using past experiences (Zhou, Chong, and Wang, 2020) . The promulgation assumes all areas of the country continue to accelerate the development of renewable energy, strengthen local absorption capacity, reduce the amount of wastewater, wind, and light, and strive to build a highly clean energy supply system (Vu, 2020) . In Shanxi, Inner Mongolia, Xinjiang, Shaanxi, and Shandong green mining technologies are expected to gradually replace traditional industries. The integration of science and technology in the field of energy development, through information technology and the introduction of a circular economy mode of production, will provide employment and opportunities and displace the traditional energy-intensive industries (He, Wei, Liu, and Zhou, 2020) . Provinces in the upper and middle reaches of the Yangtze River and other central provinces are actively seizing the opportunity of natural gas and renewable energy sources to gradually release supply capacity to the central region to improve energy cleanliness (Liu, et al, 2020b) . The 11 provinces and cities of the "Yangtze river economic belt" strive for the promotion of the country, and enterprises have formed a benign mix of industrial transformation, environmental protection upgrading, government-enterprise cooperation, and the participation of private capital (Zhuo, Guan, & Ye, 2020) . Some regions in the five regions have the self-circulation of energy production, supply, and elimination, while some regions are still dominated by external energy supply. For example, one-third of the Zhejiang province's electricity comes from outside the region (Li, Lei, Li, and Liu, 2020a) . Also, China's administrative governance has a special means, that is, the policy of poverty alleviation. This policy is not only poverty alleviation, but also has a great impact on energy production, supply, and consumption. For example, in Xinjiang and Ningxia province, the coal power supply, wind power supply, and natural gas supply have their consumption and absorption counterparts corresponding to the poverty-stricken provinces (Lei, Yao, and Zhang, 2020b ). China's urbanization process is still in the promotion stage, while urbanization plays an important role in China's energy consumption. The study of energy consumption in the process of urbanization from a spatial perspective is conducive to the coordinated development of urbanization and energy consumption (Xie, Yan, Zhang, and Wei, 2020) . In China, the previous energy problems in the process of urbanization are relatively extensive, in the future development of urbanization, the energy-saving strategy will be included in the process of J o u r n a l P r e -p r o o f urban planning and layout, starting from the demand side, the construction of economical and intensive mode of energy use, a new type of urbanization construction of ecological efficiency, energy conservation, and environmental protection, it will be China's new micro one of the symbols of the new space geographic economy (Yu, Huang, Pan, and Long, 2020 ). With the development of the Chinese government's green and environmental protection law enforcement becomes legally enforceable (Wang, 2019c) , China's energy science and technology ministries, also strengthened laws related to the mining of coal, oil and gas exploration technology, recovery of smelting technology, environmental protection, as well as aspects related to clean coal and efficient conversion utilization of feedstocks (Li, Yang, Wei, and Zhang, 2019c) . Similarly, other laws have affected energy generation from nuclear, photovoltaic, wind power, and other aspects, whether in the design, manufacturing, or operation and maintenance (Jiang, You, Merrill, and Li, 2019a) . Much of the focus has been on renewable energy, designed to stimulate technological innovation in areas of smart grid, energy storage to enable a transition to renewables and foster a new digital economy (Zhu, Fan, Shi, and Shi, 2019) . The current Chinese market reforms (Table 2B ) are designed to promote active research and development of new energy technologies and industries, particularly in green energy and transport (Elliott and Shanshan, 2008) . Both state-owned enterprises and private investors are committed to seizing the commanding heights of a new round of green and low-carbon technologies (Qian, Wang, Wang, and Chen, 2019) . China is also investing heavily into artificial intelligence, cloud computing, big data, industrial internet, new materials, the large-scale generation of blockchain, and the sinking digital marketplace where technology commercialization is matched with Angel investors has become one a major source of innovation and buy-ins (Yue, et al. 2019) . With the development of first-line terminal sensing and control technology, the production efficiency of energy production and transportation will be significantly improved. According to artificial intelligence-based prediction, the efficiency in the manufacturing sphere will be improved by 5-10 %. With the direct collaboration of machines, the large-scale intelligent transportation upgrade will be closer to people's lives (Sun and Medaglia, 2019 ). In the supply or consumption terminals, driverless new energy vehicles, intelligent traffic dispatching applications, the crossregional industrial interconnection of energy production, and cross-type and proportionally J o u r n a l P r e -p r o o f dispatching of energy consumption have made steady progress (Mann, 2019) . As shown in Table 2B , much of the focus has been on the implementation of technical assistance to reduced CO2 emissions as PM, through a transition to sustainable energy sources and digitization of the industrial economy to an industrial internet economy mirroring moves by other countries such as the USA and Russian Federation (Zhang, and Chen, 2019) . The further integration of the industrial Internet and data has been widely applied in China's domestic market, which brings new development opportunities and challenges to the energy industry (Yin, Gong, Guo, and Wu, 2019) . Based on the traditional energy industry, the energy industry will achieve great improvement by solving the "five core problems": (i) the transformation of energy digitalization, (ii) the collection of energy industry data, (iii) the value-added service technology of data comprehensive analysis, (iv) market demand, (v) and core products manufacturing & distribution (Liu, 2019) . Zhang and Wen, 2008; Sun, 2008; Chen et al. 2020; and Huang, Zhao, and Huang, 2020) . China, driven by the five-year plan has targeted environmental pollution as a major obstacle to increased efficiency and cost savings and envisions a transition to digital environmental as a benefit as approximately 80 % of all carbon dioxide emissions up to 2015 were from heavy industries (Zhou, et al. 2019) . The roll-out of artificial intelligence, industrial Internet, and blockchain, the combination of an energy revolution and digital revolution is one approach to transition to local and more responsive environmental to both supply-side but also demand economics (Li, Wang, and Zou, 2019d) . The assumptions are that through the introduction of a smart digital economy, the energy system is increasingly digital and intelligent, especially the rapid development of clean energy represented by the production and supply of new energy and renewable energy, forming a new generation of energy digital technology economy. It is embodied in the multiple sharing of energy types, the mutual crossing of the main body's source-network-load, the mutual promotion of energy consumption and information consumption, and real-time data reporting and anticipates that it will incorporate elements of cloud computing, embedded device reporting, robotics, just-in-time deliveries, and payment. Since this involves digital transactions, electrically operated devices with lower power demand the carbon footprint is anticipated to drop (Zhao, Jia, Danlei, and Shiwei, 2019) . Under the policy influence of such technology, the raw materials, manufacturing technology, control technology, and management technology involved in the energy supply side, transportation network side, and consumption load side will all undergo qualitative changes such as in the field of agriculture . At present, the technology has gradually realized the real-time identification of the supply and consumption state of different types of energy, the timely installation of various energy storage regulation technologies, the statistical analysis of the proven-network-load operating curve of each province, and the prediction and response of potential risks in advance (Jha, Kumar, Chatterjee, and Khari, 2019) . In terms of top-level management and online supervision, online data collection, transmission, and cloud computing analysis will inevitably evolve to advance new intelligent automated operations, maintenance technologies, and most importantly, the supply chain (Ben-Daya, Hassini, and Bahroun, 2019). All these new technologies, summarized in figure 5A will give birth to the Internet digital economy in the field of energy so that the energy economy is no longer the traditional asset-J o u r n a l P r e -p r o o f heavy economy, but both the traditional asset-heavy real economy and the digital asset economy. In the next five to 10 years, China's energy sector will form a new type of business and a new model powered by energy numbers (Guseva, Dzusova, and Kulikova, 2019) . According to the information released at several meetings of the financial and economic committee of the Chinese government in 2019, supply-side reform in the energy sector and the construction of an economy that emphasizes both green and quality will continue to be the keynote of the 14 th five-year plan period . With the dual promotion of the country and the market, the energy technology field will further form an industrial system upgrading that combines points, lines, and faces (Yilong, and Jiaying, 2020) . With the implementation of the "13 th five-year plan" in the field of energy, how to build a high-quality green energy system reform transition, from sustained growth to more of a balanced holistic strategy in the "14 th five-year plan" is the central policy question which will occupy managers and decision-makers, as China continues to update part of its energy planning portfolios and specific policies seven In the "14 th five-year plan", to maintain energy consumption more emphasis will be given to production and distribution from various energy sustainable sources, with a local mix of Solar PV, wind, it is anticipated that energy efficiency will improve requiring fewer coalpowered stations and thereby reducing carbon emissions and energy use costs, and promoting market-oriented energy trading of wind and solar companies even if electricity consumption continues to rise (Lo, 2020) . The State Council directives prioritize the production of clean and efficient utilization of petrochemical energy and the large-scale promotion of nuclear energy and renewable energy, building on from the best practices of the previous plan (Yan and Su, 2020) . Based on the report card of energy conservation and emission reduction, the directive empowers the promotion of in-depth energy conservation and energy efficiency technologies. In terms of the reform of energy science and technology system, the directives also have setaside funding, tax adjustments to further develop clean technologies and IoT integration such as the battery industry chain and the hydrogen energy industry chain is also continuously trying to adopt more flexible development policies and encourage the participation and development of various entities (Jiang et al, 2020a; Li, 2019e; and Jingyu, et al. 2020 ). With the continuous development of the new normal of China's economy, China's energy development has entered the "three lows" trend. Some of these are summarized in figures 5b and 5C. Energy development is characterized by "low growth rate, low increment, and low carbonization", and the Chinese government's continuous tightening of "constraints on the safe supply of resources, the protection of the ecological environment and the reduction of greenhouse gas emissions" has been further strengthened (figures 5D-5F). During the period of the 14 th five-year plan period, the carbon intensity of Chinese provinces is expected to continue to decline significantly as electric vehicles and renewables kick-in. The Chinese government is still the same as usual, on the demand side strongly advocated and encouraged revolution, the energy consumption in response to an increase in demand for energy, economic growth, and urbanization through the upgrade of industrial structure development of high and new technology industries, low energy consumption through realtime pricing, peak shaving, demand response to the demand side of the energy management, enhance the energy market competition mechanism, revitalize the enterprise vitality, eliminate backward production capacity, improve the efficiency of energy production enterprise for production (Trubnikov, and Richter, 2020) . Whilst the policy directives are set forth at the State Council, the actual implementations are left to the individual provinces. For example, clean energy, or the proportion of non-water renewable energy is achieved by wind or solar power, in the form of an integrated energy system and where systems can complement each other, promote energy system step by step in the direction of clean, green, low carbon transformation (Sayigh, 2020) . In the comprehensive energy system, the traditional fossil energy such as coal power needs to be phased-out with wind power, photovoltaic power, and other renewable energy, and the proportion of renewable energy needs to be gradually increased, to reduce sufficient time for maturation of technologies and develop high storage capacities with cheaper operating costs (Li, and Taeihagh, 2020b) . The industrial Internet has been widely used in the field of energy and has penetrated and affected the integrated development of the secondary and tertiary industries covered by energy (Shackelford, 2020) . Under the influence of blockchain technology based on the industrial Internet, the energy production relationship that can be reconstructed with the characteristics of decentralization in the digital economy era will gradually come to displace centralized systems and enhance redundancy (Hou, Wang, and & Luo, 2020) . This new technology of integrated development will probably reshape the status and interrelationship of various subjects in the field of energy production, change the form of product distribution, and become a new engine to drive the development of energy digital economy (Bai, Cordeiro, and Sarkis, 2020b ). Today's digital economy era based on blockchain softens the boundary between the producer, and end-user and the production materials no longer belong to a single party, as the "producer-consumer" linage is not strictly descriptive. In the field of energy digital economy, blockchain is profoundly changing the management, trading, and operation of distributed energy, and demand-side users are gradually playing the dual roles of consumers and producers (Bai, and Sarkis, 2020c) . This aspect makes the energy supply-side and demand-side are the support of information technology, each data source, which changes the original traditional centralized energy distribution network and center, formed the new smart energy system construction direction, on the other hand, can complement each other, send parallel this new type of integrated energy storage mode to adapt to the market demand (Saberi, Kouhizadeh, Sarkis, and Shen, 2019) . With the acceptance and promotion of the market, the energy and J o u r n a l P r e -p r o o f digital resources supported by cloud technology will get the opportunity of coordinated development. Surely, safety and reliability are still a problem that needs to be addressed before widespread adoption and replaced the traditional production workflow (Abeyratne, and Monfared, 2016) . Methanol synthesis through CO2 hydrogenation offers an attractive way to generate a synthetic precursor molecule, a fuel substitute, and a mechanism to lower the global CO2 threshold (Zangeneh, Sahebdelfar, and Ravanchi, 2011) . The economy of such an approach depends on whether the price of electricity is cheaper from coal, natural gas, solar, nuclear, or wind and are on average more expensive than conventional approaches. The conversion of CO2 to methanol is also more expensive (~€650 per ton vs €400 per ton) than the syngas process, although the price difference is decreasing, like how the price decrease from solar sources (Jarvis, and Samsatli, 2018) . The higher prices reflect the high stability of carbon dioxide and its associated activation (1072 kJ/mol) and water production as a side-reaction which can lead to the deactivation of metal catalysts such as copper. One approach to minimize these potential disadvantages is to utilize the reverse water gas shift reaction which is separated from the main methanol synthesis route and then combined in the reactor. One final advantage is that net carbon dioxide emissions from hydrogenation are lower than from syngas emissions (0.2-tons CO2 per ton CH3OH, versus 0.8-ton CO2 per ton CH3OH) (Din et al. 2019 ). The synthesis, operational parameters, and common catalyst configurations are summarized. Methanol has several advantages as a fuel, due to its energy content 726.3 kJ/mol, although its heat of combustion per gallon is lesser than gasoline (57,520 Btu versus 116,090 for gasoline) (Liu, and Ma, 2009) . Methanol is also a viable fuel substitute as their prices per gallon are similar with methanol being slightly cheaper ($1.50/gallon versus 1.71 for a gallon, Jan 2020), is a liquid at room temperature and has a lower freezing temperature than standard gasoline (-96 C versus -57 C for n-octane, although the value will depend on other additives) (Carr, and Riddick, 1951) . Methanol having less carbon than gasoline combusts to only carbon dioxide and water, and has a lower flash point (14 C versus 13.3 C for n-octane, although in typical gasoline with additives the flashpoint may be negative (~ 43 C) and in this regards is a safer fuel choice. Since gasoline can exhibit incomplete combustion products and particulate matter, J o u r n a l P r e -p r o o f inhalation of fumes from the combustion of gasoline is generally more toxic than for methanol (Ghiotti, and Boccuzzi, 1987) . Methanol is synthesized commercially by syngas using zinc/chromic based catalysts at 300 C and 296 atm. Substitution of Zinc/Chromic by Cu/ZnO has enabled the synthesis to be favorable at lower pressures and temperatures (49-296 atm, 200-300 C) (Rico et al. 2010 ). The present method for synthesis is related to the use of syngas and CO2 over the Cu-ZnO/Al2O3 catalyst at 220-300 C and 46-96 atm respectively (Weigel, Koeppel, Baiker, and Wokaun, 1996) . Methanol seed material is carbon dioxide with carbon monoxide as surface oxygen, which is an attractive feature as it consumed CO2 and has been proposed as a potential avenue away from the carbon economy to more clear methanol and ethanol economies, whereby methanol synthesis is via hydrogenation of CO2 driven by solar or geothermal energy, at 250 C and 29 atm. In catalyst design, the three major obstacles are thermodynamic, kinetic, and cost considerations (Yang, and Jackson, 2012) . As CO2 is a stable molecule, high pressures, and temperatures around 250 C are required to drive the reaction forward (Eqn: 2), although the heat of formation suggests the reaction is favored at lower temperatures (Gallucci, Paturzo, and Basile, 2004) . CO2 + 3H2  CH3OH +H2O H298K = -49.5 kJ/mol (2a) Therefore, the actual pressure and temperature regime is influence by the catalyst employed. Recently CO2 hydrogenation to methanol using a Cu/ZnO/Al2O3 catalyst was achieved ay 49 atm and at 296 atm when using a Ni(CO)4 catalyst. One problem is water formation that leads to the deactivation of the catalyst, in addition to the use of hydrogen, which is greater than by syngas alone. Water can also act as an oxidant at higher temperatures and oxidize the metal to the metal oxide (Mahajan, and Goland, 2003) . The water can be removed during the reaction, or CO introduced to reduce the metal oxide. This would regenerate the CO2, or H2 gas been used for the reduction of CuO to Cu. recently a new study showed that pre-addition of water suppressed the oxidation process, similar to the effects of water addition for CO selectivity by the reverse water gas shift reaction (Li, Yuan, and Fujimoto, 2014) . This reaction: CO2 + H2  CO + H2O H298K = 41 kJ/mol (2d) is unfavored, thereby requiring higher temperatures to drive it, which also promotes the reverse J o u r n a l P r e -p r o o f water gas shift relative to hydrogenation of CO2 to methanol. The current approach focuses on liquid phase methanol synthesis rather than gas-phase methanol hydrogenation (Samimi, Hamedi, and Rahimpour, 2019) . The major metal catalyst for methanol synthesis is based on copper, zinc oxide, and alumina (Yang, et al. 2006 ). Silver as the active catalytic component with ZrO2 compared with Cu/ZnO2 at temperatures lower than 230 C, with enhanced selectivity for CO2 hydrogenation, when added to Cu/ZnO2 with 100 % selectivity whereas the selectivity with Cu/ZrO2 was 95 % (Köppel, Stöcker, and Baiker, 1998) . Although the selectivity of silver is greater its activity is not as high as with CuO/ZrO2 catalyst (Grabowski, et al. 2011) . Palladium based catalysts at 119 atm and 350 C n over La2O3 support, but with lower selectivity for the CO2 hydrogenation reaction (~ 90 %) (García-Trenco, et al. 2018) . Palladium (Pd) on in catalyst also gave superior results relative to Cu/ZnO/Al2O3 catalyst. Other supports evaluated were Pd on CeO2 at 500 C and multi-walled carbon nanotubes supposed Pd/ZnO or Pd/TiO2 at 500 C gave higher selectivity due to stronger interactions between the metal catalyst and the support surface (Liang, Dong, Lin, and Zhang, 2009 ). In some of these studies, lower temperatures resulted in the production of methane, with indications that their selectivity for methanol may be greater than methanol (Shen, Okumura, Matsumura, and Haruta, 2001) . Copper is the most widely used catalyst particularly when supposed by ZnO and is operated at higher temperatures than 250 C, 52 atm (Behrens, 2014) . By using ZnO on silica the methanol formation from H2 and CO2 can be increased, due to the availability of oxygen vacancies of zinc oxide, improving both stability and dispersion of the copper catalyst (Sugawa, Sayama, Okabe, and Arakawa,1995) . Therefore, the addition of support that enhances the stability of copper whilst increasing its dispersion generally leads to greater methanol selectivity (Ovesen, et al. 1997 ). The addition of Ga2O3 to Cu/ZnO led to better catalyst performance for hydrogenation of CO2 to methanol, where the Ga2O3 facilitate the reduction fo Cu, increasing the activity, suggesting that the interaction of Cu with ZnO support is greater than with the SiO2 support. Whilst methanol is generated using copper alone, the addition of a promoter like Ga2O3 or support such as CeO or ZnO, because of the latter offer the probability of greater dispersion of Cu on the support and thereby greater catalytic surfaces for the hydrogenation reaction to take place, relative to copper alone, in addition to stabilizing effect of the support material for the copper (I) species (Toyir, de la Piscina, Fierro, and Homs, 2001) . This reflects the complexity of the system in terms of catalyst half-life, selectivity, and activity, resulting in Cu/ZnO/Al2O3 or Cu/ZrO2 as being the default choice for the hydrogenation reaction (Liu, Lu, and Yan, 2005) . The oxidation state of the metal catalyst is critical, it is generally observed that the zero-valent species are more stable and active. Other support systems evaluated were silica, alumina, and zirconia, due to the availability of accessible oxygen sites and ion exchange pricing multiple reactive surfaces for the hydrogenation reaction. therefore, the correct choice of promoter and support can lead to greater activity, for example, Cu/ZrO2 over Cu/ZnO (Nitta, et al. 1994) . Zirconia can form some crystalline forms that are transformed at various pH, with the tetragonal form of zirconia is the most stable at basic pH environments, while at neutral pH the monoclinic form of zirconia is the most stable (Zhuang, Bai, Liu, and Yan, 2010) . Lastly, the calcination temperature can also influence the allotropic, with the tetragonal form being most stable under 500 C, but the monoclinic being formed at higher temperatures (Rhodes, and Bell, 2005) . The monoclinic zirconia (mZrO2) is more active than the tetragonal allotrope (tZrO2), due to greater interactions of the tetragonal form with intermediates than the monoclinic formation (Jung, and Bell, 2002) . Doping with silver ion has also been shown to enhance activity via stabilization of the tZrO2 form, suggesting that Cu/ZrO2 is a better catalyst than Cu/ZnO. The addition of ZrO2 or ZnO generally increased the activity of the Cu catalyst by increasing the stability of the Cu ion, but the rate was unchanged with ZnO but not ZrO2 with doped Ag + (Grabowski, et al. 2011) . This difference between ZnO and ZrO2 appears to be due to the stabilizing effect of ZrO2 on Ag + that is lacking with ZnO. The pH-dependence for the hydrogenation reaction may be related to the mechanism of co-precipitation for Cu/ZnO/Al2O3 due to aging, where hydroxide ions are release increasing the pH. The increase of pH can be countered by the addition of CO2, and a constant pH improves catalyst performance (Bems, et al. 2003) . H2O + CO2  2H + + CO3 2-(3b) Thus, methanol selectivity is highly dependent upon the Cu surface, morphology, and the phase of ZrO2 (Guo, et al., 2011) , summarized in Table 3A . J o u r n a l P r e -p r o o f The introduction of CO2 in the aging process has several advantages, which are control of composition (Purohit, Sharma, Pillai, and Tyagi, 2001) , maintenance of constant pH (Baltes, Vukojević, and Schüth, 2008 , increased in pore volume to promote gas diffusivity and increase surface area to promote catalysis (Guo, et al. 2011 ) in addition to strong interactions between Cu and specific stable phase of ZrO2 (Zhuang, Bai, Liu, and Yan, 2010) . The above studies with glycine or co-precipitation suggest that crystallinity and activity of the copper catalyst are counter to each other, where the dopant atom (e.g. Ag) serves as a site for nucleation Cu crystallization (Maniecki, et al. 2011) . The extent of crystallization, in turn, depending on the degree of dispersion of the dopant or alloyed metal or metal substitution (e.g. La for Cu) (Guo, et al. 2011) , with activity being correlated with Cu active sites (Zhang, Zhang, and Chen, 2012) and selectivity being correlated with basic sites on the catalytic surface (Yoneyama, 1997) , as shown in Table 3B . As observed in earlier studies, the addition of Ga2O3 as a catalyst promoter increased activity, could be used instead of substitution of the metal catalyst itself. the promoter could enhance the catalyst to support structure or stabilize the metal catalyst itself by acceptance of an electron or promoting the reduction of the active metal (Liu, Lu, and Yan, 2005) . As stated, earlier gallium oxide enhanced the activity of copper-based catalysts via oxidation of copper (0) to copper (I), thereby maintaining a constant ratio between eh zerovalent and mono species increasing the catalyst half-life (Toyir, et al. 2011) . Niobium oxide (Nb2O5) as support has also been used and has been shown to exhibit excellent activity and selectivity in the hydrogenation reaction fo CO and CO2 for methanol production (Furukawa, et al. 2011) . As this is an acidic oxide, it can also be used as a promoter. It is thought that the oxide increases Cu dispersion, enhancing surface area sites better Cu stability against water, and enhanced activity with CO2 hydrogenation (Hu, Kunimori, and Uchijima, 1991) . Zinc oxide has been used as a catalyst in the CO2 hydrogenation reaction, and as a promoter for Cu by increasing its dispersion, thereby slowing potential agglomeration on the active copper catalyst when supported by alumina (Saito, Fujitani, Takeuchi, and Watanabe, 1996) . The zinc oxide is basic and can counteract the activity of the alumina support. This has been shown to slow down the conversion of methanol to dimethyl ether (Toyir, et al. 2001 ). The interaction between Cu and ZnO is thought to occur via interaction interactions Cu + . O-Zn, where the zinc oxide can adsorb H2 species and promote a stable intermediate (methoxy oxide) which is ultimately converted to methanol upon hydrogenation (Kanai, et al. 1996) . It should be noted that with syngas based synthesis, the feed gas may have trace amounts of sulfur that can position that active catalyst surface, ZnO is thought to be able to abstract the sulfur forming ZnS and thereby lessening the deactivation of the Cu species (Centi, and Perathoner, 2013 ). The Zn was also able to adsorb with species such as HxCO, increasing the rate of methanol synthesis (Chen, et al.1999 ). The role of the catalyst support is the dispersal of the active metal, but also to avoid sintering or aggregating the metal particles. The acidity or basicity of the support will affect catalyst performance (Wang, Wang, Ma, and Gong, 2011) . Silica has high thermal stability and good dispersion capacity and has been used as a support material using CO2 and H2. Some first two and second-row transition metals were evaluated ion silica supports, at 250 C and 49 atm resulting in higher selectivity of methane J o u r n a l P r e -p r o o f for Ni, Co, and CO on Pt (Sugawa, Sayama, Okabe, and Arakawa, 1995) . For methanol selectivity, Cu, Ag, Fe, and Pd were greater and may diver higher activities due to the greater surface area of silica relative to ZnO. Silica can also transform silica hydroxide in the presence of steam, resulting in a search for substitutes such as alumina (Takahashi, et al. 2004 ). Alumina has been used as a support for methanol by CO2 hydrogenation using Cu/ZnO. However, over a prolonged operation that methanol yields have decreased, which could be lessened by the addition of Cu/ZnO/Al2O3 (Centi, and Perathoner, 2013) . Zirconia has been used as a support with Cu (ZuO) which gave good selectivity and stability that could be increased by the addition of Al2O3 as a Cu/ZnO/ZrO2/Al2O3 system, The higher thermal stability of ZrO2-Al2O3 and selectivity of Cu(0)ZrO2 may be the reason or the improvement Also, the Cu/ZnO/ZrO2 system was found to be more tolerant to water poisoning during methanol synthesis than Cu/ZnO/Al2O3 (Li, Yuan, and Fujimoto, 2014) . Recently carbon nanotubes or fibers have been used due to the high surface area and thermal stability of carbon and the ability to adsorb hydrogen via H-adsorption sites. Catalyst particles dispersed on CNT support gave more active sites than on activated carbon, resulting in increased hydrogenation of methanol (Liang, Dong, Lin, and Zhang, 2009) . Low rates were observed for Pd/CNT suggesting that Pd atoms required to be activated for the hydrogenation reaction to proceed and require a nearby metal oxide. Nanocarbon fibers have also been used and can promote the hydrogenation to methanol from CO2 at lower temperatures (Wang, Lu, Li, and Li, 2015) . Whilst the macro-level mechanism is known in that CO2 adsorption on metal oxide and H2 on metal, with the formation of intermediates being the rate-determining step in methanol synthesis through CO2 hydrogenation on copper (Rasmussen, et al. 1994) . The active species appears to be Cu (0), although other studies also suggest that Cu(I) stabilized on the catalyst (Cu(0)) surface also assists with the CO2 adsorption and has a bearing on methanol selectivity as well as activity (Liu, Lu, and Yan, 2005) . This stabilization may also assist with the (Chen, et al. 1999 (Herman, et al. 1979) . Also, studies on Cu/ZnO/Al2O3 show that after adsorption of oxygen and carbon dioxide, carbonate (CO3) and formate (HCOO) are generated as intermediates, with the carbonate being converted to formate upon additional hydrogenation, forming a methoxy species (CH3-O) and methanol on the final reduction step (CH3-OH) (Fujitani, and Nakamura, 2002) . Using Pd/Ga2O3 only these two species were identified when CO2 was reduced to methanol, whilst the major species are formate, minor species often identified are varied such as carboxylate (HOOCH) and methylene peroxide (CH2OO) (Sahki, et al.2011 ). The formate is coordinated with the surface metal oxide axially with an adjacent adsorbed carbon dioxide and hydrogen from the metal, with the monodentate formate being unstable at temperatures over 200 C and is transformed into formic acid (HCOOH) upon a reaction with the newly formed formate (Jiang, et al. 2019b) . is generated with upon hydrogenation yields formic acid, which in turn undergoes dehydration to product methylene peroxide (CH2OO) (Arena, et al. 2008) . The unstable methylene peroxide is converted to the methoxy species through reaction with adsorbed hydrogen (H2) and to methanol upon reduction. The application of bimetallic catalysts such as Cu/ZnO and Cu/ZrO2 suggest a dual mechanism operating on each catalyst surface, whereby CO2 hydrogenation occurs on the metal surface with adsorbed hydrogen (H2) and carbon dioxide adsorption on the metal oxide, with molecular hydrogen adsorption occurring on the copper atoms. Upon adsorption the hydrogen molecules dissociate to form atomic hydrogen and are transported from the Cu surface to the ZrO2 surface where CO2 is adsorbed by spillover, to reduce adsorbed CO2 to formate, methyl species and reduction to methanol (Gao, and Au, 2000) . In cases of metal oxide supports, the optimal ratio is not uniform, for example for Cu on ZnAl2O4, the Cu: ZnO ratio of 0.72 was found to yield the greater activity, whilst for Al/Zn the ratio was 0.5, which reflects sites for synthesis and sites for coordination via monodentate or bidentate formate hydrogenation to methanol via a methoxy intermediate (Frank, et al. 2007 ). With copper substitution by La, the range for a higher activity for LaMn1-xCuxO3 (0 ≤x ≤), with a modal value of 0.5. The range like with Ag + stabilization that activity is related to the dispersion of Cu + species that is inhibited by the reduction of Cu + to Cu 0 , which is no longer stabilized by Mn in the perovskite (Jia, Gao, Fang, and Li, 2010 (Ahmed, Shibata, Taniguchi, and Izumi, 2011) . The catalyst in the forms of beads or pellets can be fixed to the surface in the form of fixed bed reactors, or suspended in a solvent which allows for thermal motion, a form of a slurry reactor which may be charged and then discharged ('digital') or steady-state ('analog') configuration (Nitta, et al. 1994 ). In general, fixed-bed reactors are applied to gas phase reactions, where hydrogenation of carbon dioxide to methanol occurs, from 200 C to 8 atm, using Cu/ZrO2/ZnO catalyst. Higher conversion may be achieved by switching over to a different catalyst such as CuZnGa or a coprecipitated Cu-Zn-Zr with gel-oxalate to provider greater active surface sites relative to coprecipitation with sodium carbonate and coordination with citric acid (Gao, et al. 2013a ). The activity of methanol synthesis is related to the number of exposed sites on the Cu surface, whilst selectivity was related to the number of basic sites on the support. The introduction of an electronegative atom may improve activity as was demonstrated by the introduction of fluorine on CuZnAl catalyst for CO2 hydrogenation to methanol (Gao, et al. 2013b) . The advantages of a fixed bed configuration are that gas and metal interaction does not require prior mixing, diffusion of reactants does not occur, and the higher volumetric loading of the catalyst and easier to upscale to higher quantities (Sherwood, and Farkas, 1966) . The deactivation of the catalyst at higher temperatures over time is one disadvantage, (Bartholomew, 2001) which may be overcome with new catalysts such as Mo2 coated by nitrogen and sulfur co-doped carbon (NSC) that as functional after almost 100 h of operation on steam (Han, Geng, Xiao, and Wu, 2019) . It was further demonstrated that Co/Mn catalyst exhibited a selectivity of approximately 49 % at 250 C for 400 h on steam, and might indicate that a bifurcated reactor design be implemented with separate hydrogen (H2) and water (H2O) feed to pre-select the optimal ratio (Stangeland, Kalai, Ding, and Yu, 2019) . In a slurry reactor, the reaction is carried out in a liquid phase, such as the operating temperature can be reduced to promote the thermodynamic reaction to the right. In this manner, the catalyst deactivation observed at elevated temperatures can be minimized. The selectivity and activity of CO2 hydrogenation to methanol was found to be greater with a slurry reactor than a fixed bed reactor design (Kim, et al. 2013) . As the reaction occurs in solution, the rate J o u r n a l P r e -p r o o f of heating, over-temperature, the temperature gradient can be controller with greater precision than with a fixed bed reactor design. In a slurry, the metal catalyst can be dispersed in the form of a powder rather than pellets and are configured in three type configurations. type 1 configuration is used for batch reaction stirred autoclaves, type 2 pump stirred, and type 3 reactant gas used to stir the mixtures (Cybulski, Stankiewicz, Albers, and Moulijn, 1999) . In the slurry, the excess heat is absorbed by the solvent, such as tetrahydroquinoline (C9H11N), which can be operated at less than 425 C and 138 atm (Sun, et al. 2002) . The role of solvent is important, as well as co-additives in determining final operating temperature, pressure, activity, and selectivity (Shreiber, and Roberts, 2000) . As hydrogenation fo CO2 to methanol is exothermic, thermodynamically, lower temperatures are favored. in practice, higher temperatures are utilized to give the gas and intermediate enough kinetic energy to interact and higher temperatures yield higher activity, up to where the equilibrium constant decreases with increasing temperature (Le Valant, et al. 2015) . The maximum temperature at which the equilibrium constant will decrease depending on the catalyst type, form, and support material but is from 220-250 C (Fujitani, and Nakamura, 2002) . This is due to the occurrence of side reactions or the reverse water gas shift reaction, which appears to have faster reaction kinetics than methanol synthesis concerning temperature (Gallucci, and Basile, 2007) . To illustrate the difference between reverse water gas shift reaction (Jiang, et al. 2020b) and methanol synthesis, the most common reaction conditions are summarized in Table 3C (for reverse water gas shift reaction) and 3D (methanol synthesis). (4) suggesting an upper limit of 250 C, above which CO2 is in part converted to CO lessening the methanol yield (Ahouari, et al. 2013) . The methanol synthesis via hydrogenation also appears to be more sensitive to temperature fluctuations than the reverse water gas shift reaction as can be seen by comparison of operating condition variance between the two (table 3A versus 3B variables) reactions (Qi, Zheng, Fei and Hou, 2001) . At 350 C, the probability of methane formation is high. Similarly, the selectivity of methanol decreased from approximately 38 % at 220 C to 2 % at 300 C (Graaf, and Winkelman, 2016) . Therefore, the optimal temperature s appears to be between 220-250 C but is highly dependent on the catalyst (Xin, Yizan, Zhang, and Jinfu, 2009 ). While the thermodynamic yield favors lower temperatures, the thermodynamic calculations point to higher pressures for the reduction reaction, with the reverse water gas shift reaction would decrease at higher pressures (Jun, Shen, and Lee, 1999) . Higher pressures also favor oxygenated byproducts such as dimethyl ether, with additional safety concerns of chambers at very high pressure. Most pressures are from 18 atm to 50 atm using Cu/Zn/Al/Zr fibrous catalyst or Cu/Al2O3 or Cu/ZnO/Al2O3 catalysts in a slurry reactor at 250 C (Liaw, and Chen, 2001 ). J o u r n a l P r e -p r o o f The stoichiometric reaction indicates one mole of carbon dioxide to three molecules of hydrogen (H2) gas, thus a ratio of (H2: CO2) of 3 is favored for CO2 hydrogenation to methanol (Bansode, and Urakawa, 2014) . In reactor practical applications it has been demonstrated that at higher pressure, the reaction is controlled thermodynamically with a ration of CO2: H2 of >10, but at lower pressures, it is kinetically controlled (ratio < 10), with a suboptimal ratio between 3-10 depending on the final pressure (Shen, Jun, Choi, and Lee, (2000) . Computational calculations at a fixed pressure (28 atm) but at varied temperatures (200-280 C) or fixed temperature (240 C) but at varied pressures (9-89 atm) show a linear relationship between H2: CO2 ratio and methanol yield (Kim, et al. 2003) . In a slurry reactor, an increase of the H2: CO2 ration from 2-5 resulted in higher CO2 conversion due to the availability of hydrogen to promote hydrogenation and methanol synthesis (Potočnik, Grabec, Šetinc, and Levec, 2000) . A problem could also be viewed as an opportunity to be solved. In the current situation of the global epidemic, digital technology plays an irreplaceable role in social life and is also exerting a profound impact in the field of energy. The Chinese government is making efforts to promote technological upgrading in the energy sector through policies and the market, especially in the integration of energy expertise and digital technology, as well as energy conservation and environmental protection technology and digital technology, to create an energy ecology based on local conditions, wisdom and comprehensively in energy-using, and security with science and technology. One technological approach is carbon dioxide hydrogenation to methanol via homogenous catalysis, which was inefficient due to lower catalyst recovery and regeneration. Consequently, heterogeneous catalysis has been adopted using a reverse water gas shift reaction, whereby carbon dioxide and hydrogen gases are converted to carbon monoxide and water by the water gas shift reaction and the resulting gas mixture of CO/CO2/H2 is channeled into a slurry reactor after removing water. The recent introduction of Cu/ZnO based catalysts indicates higher selectivity and activity to methanol than prior approaches due to operation near-optimal thermodynamic conditions such as low temperature and moderate pressures and remove off heat due to efficient heat removing solvent. Whilst direct CO2 hydrogenation to methanol is a new technology, advances in a catalyst, reactor design, and operational at lower temperatures are pushing these technologies to be competitive with electricity generation from fossil fuels, J o u r n a l P r e -p r o o f with the catalyst being based around Cu, such as Cu/ZnO, Nb2O5 of Ga2O3, with carbon nanotubes as support. Due to the exothermic profile of the reaction, low temperature and high pressure will favor methanol selectivity over methane or other by-products, due to depression of the reverse water gas shift reaction and methanol decomposition. The stoichiometric ratio of H2: CO2 is 3 is also favored for the hydrogenation reaction, but practical applications have a ratio of 3-10. Dr. Gao conceived the thrust and wrote the first draft. Dr. Liu did figures 1,4 and 5 and the section on catalysis. Lastly, Dr. Bashir contributed to the analyses of emission data, catalytic technologies, figure 3 , and references and copyright. Two of the authors are from TAMUK (Drs. Sajid Bashir and Jingbo Liu) and Dr. Liu is also a Guest Editor. However the manuscript will still go through the peer-review process. The role of the State Council Modern Economic Growth in India and China: The Comparison Revisited, 1950-1980. 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Managing Cybersecurity and Data Privacy Risks in the Industrial Internet of Things How to improve the competitiveness of distributed energy resources in China with blockchain technology Blockchain technology: Business, strategy, the environment, and sustainability A supply chain transparency and sustainability technology appraisal model for blockchain technology Blockchain technology and its relationships to sustainable supply chain management Blockchain ready manufacturing supply chain using a distributed ledger Technologies and infrastructures underpinning future CO2 value chains: A comprehensive review and comparative analysis Recent developments on heterogeneous catalytic CO2 reduction to methanol The analysis of the energy and environmental impacts of microalgae-based fuel methanol in China Physical properties of the methanol-water system Chemical and physical properties of copper-based catalysts for CO shift reaction and methanol synthesis Evaluation of different dielectric barrier discharge plasma configurations as an alternative technology for green C1 chemistry in the carbon dioxide reforming of methane and the direct decomposition of methanol Surface species in CO and CO2 hydrogenation over copper/zirconia: on the methanol synthesis mechanism China's growing methanol economy and its implications for energy and the environment An experimental study of CO2 hydrogenation into methanol involving a zeolite membrane reactor Integrating low-temperature methanol synthesis and CO2 sequestration technologies: application to IGCC plants Development of a highly stable catalyst for methanol synthesis from carbon dioxide Green methanol production process from indirect CO2 conversion: RWGS reactor versus RWGS membrane reactor Methanol synthesis from CO2-rich syngas over a ZrO2 doped CuZnO catalyst Copper-and silver-zirconia aerogels: preparation, structural properties, and catalytic behavior in methanol synthesis from carbon dioxide Influence of polymorphic ZrO2 phases and the silver electronic state on the activity of Ag/ZrO2 catalysts in the hydrogenation of CO2 to methanol PdIn intermetallic nanoparticles for the hydrogenation of CO2 to methanol Carbon nanotube-supported Pd-ZnO catalyst for hydrogenation of CO2 to methanol The influence of the support on the activity and selectivity of Pd in CO hydrogenation Heterogeneous catalysis of CO2 conversion to methanol on copper surfaces Methanol synthesis from CO2 and H2 over silver catalyst. Energy Conversion and Management Kinetic implications of dynamical changes in catalyst morphology during methanol synthesis over Cu/ZnO catalysts Highly effective conversion of CO2 to methanol over supported and promoted copper-based catalysts: influence of support and promoter Nanocrystalline zirconia as a catalyst support in methanol synthesis Copper-zirconia catalysts for methanol synthesis from carbon dioxide: Effect of ZnO addition to Cu-ZrO2 catalysts The effects of zirconia morphology on methanol synthesis from CO and H 2 over Cu/ZrO 2 catalysts: Part I. Steady-state studies Effects of zirconia phase on the synthesis of methanol over zirconia-supported copper Relations between synthesis and microstructural properties of copper/zinc hydroxy carbonates The influence of La doping on the catalytic behavior of Cu/ZrO2 for methanol synthesis from CO2 hydrogenation Ultrafine ceria powders via glycine-nitrate combustion Correlations between synthesis, precursor, and catalyst structure and activity of a large set of CuO/ZnO/Al2O3 catalysts for methanol synthesis Structure and performance of Cu/ZrO2 catalyst for the synthesis of methanol from CO2 hydrogenation Bimetallic Au-Cu, Ag-Cu/CrAl3O6 Catalysts for Methanol Synthesis Effect of promoter SiO2, TiO2, or SiO2-TiO2 on the performance of CuO-ZnO-Al2O3 catalyst for methanol synthesis from CO2 hydrogenation Photoreduction of carbon dioxide on quantized semiconductor nanoparticles in solution Solvent-free aerobic alcohol oxidation using Cu/Nb2O5: green and highly selective photocatalytic system Interaction of hydrogen and oxygen with niobia-supported and niobia-promoted rhodium catalysts Development of copper/zinc oxide-based multicomponent catalysts for methanol synthesis from carbon dioxide and hydrogen The synergy between Cu and ZnO in methanol synthesis catalysts Advances in catalysts and processes for methanol synthesis from CO2 Synergism between Cu and Zn sites in Cu/Zn catalysts for methanol synthesis Recent advances in catalytic hydrogenation of carbon dioxide Addition of zirconia in Ni/SiO2 catalyst for improvement of steam resistance A remarkable difference in CO2 hydrogenation to methanol on Pd nanoparticles supported inside and outside of carbon nanotubes Methanol synthesis on Cu (100) from a binary gas mixture of CO2 and H 2 Catalytic synthesis of methanol from COH2: I. Phase composition, electronic properties, and activities of the Cu/ZnO/M2O3 catalysts Methanol synthesis from CO and CO2 hydrogenations over supported palladium catalysts CuO/ZnO/Al2O3 catalyst. Reaction Kinetics, Mechanisms, and Catalysis hydrogenation to methanol on PdCu bimetallic catalysts with lower metal loadings Solid-state interactions, adsorption sites, and functionality of Cu-ZnO/ZrO2 catalysts in the CO2 hydrogenation to CH3OH CO2 hydrogenation to methanol on a YBa2Cu3O7 catalyst Steam reforming of methanol over copper-containing catalysts: Influence of support material on microkinetics Influence of copper content on structural features and performance of pre-reduced LaMn1-xCuxO3 (0≤ x< 1) catalysts for methanol synthesis from CO2/H2 Photocatalytic conversion of carbon dioxide into methanol using zinc-copper-M (III)(M= aluminum, gallium) layered double hydroxides Influence of Zr on the performance of Cu/Zn/Al/Zr catalysts via hydrotalcite-like precursors for CO2 hydrogenation to methanol Influence of fluorine on the performance of fluorine-modified Cu/Zn/Al catalysts for CO2 hydrogenation to methanol Studies of the slurry reactor Mechanisms of catalyst deactivation High selective synthesis of methanol from CO2 over Mo2C@ NSC Mesoporous manganese-cobalt oxide spinel catalysts for CO2 hydrogenation to methanol Promotion of CO2 hydrogenation to hydrocarbons in three-phase catalytic (Fe-Cu-K-Al) slurry reactors Monolithic reactors for fine chemical industries: a comparative analysis of a monolithic reactor and a mechanically agitated slurry reactor Liquid/catalyst interactions in slurry reactors: changes in tetrahydroquinoline composition during methanol synthesis over zinc chromite Methanol dehydrogenation in a slurry reactor: evaluation of copper chromite and iron/titanium catalysts The Cu-ZnO synergy in methanol synthesis from CO2, Part 1: Origin of the active site explained by experimental studies and a sphere contact quantification model on Cu + ZnO mechanical mixtures A theoretical analysis of methanol synthesis from CO2 and H2 in a ceramic membrane reactor Recent Advances in Carbon Dioxide Hydrogenation to Methanol via Heterogeneous Catalysis Catalytic activity of the M/(3ZnO· ZrO2) system (M= Cu, Ag, Au) in the hydrogenation of CO2 to methanol CO2 hydrogenation to methanol over CuZnGa catalysts prepared using microwave-assisted methods Copper-Gallia interaction in Cu-Ga2O3-ZrO2 catalysts for methanol production from carbon oxide (s) hydrogenation Fluorine-modified Zr catalysts via hydrotalcite-like precursors for CO2 hydrogenation to methanol Hydrogenation of CO2 to CH3OH over Cu/ZnO catalysts with different ZnO morphology Methanol synthesis from CO2 hydrogenation over Cu/γ-Al2O3 catalysts modified by ZnO, ZrO2, and MgO Bimetallic Pd-Cu catalysts for selective CO2 hydrogenation to methanol Study of CuZnMOx oxides (M= Al, Zr, Ce, CeZr) for the catalytic hydrogenation of CO2 into methanol Cu/Zn/Al/Zr catalysts via phase-pure hydrotalcite-like compounds for methanol synthesis from carbon dioxide Methanol synthesis from CO2 hydrogenation over La-M-Cu-Zn-O (M= Y, Ce, Mg, Zr) catalysts derived from perovskite-type precursors Methanol synthesis from CO2 hydrogenation over copper-based catalysts Low-temperature methanol synthesis catalyzed over Cu/γ-Al2O3-TiO2 for CO2 hydrogenation Chemical equilibria in methanol synthesis including the water-gas shift reaction: a critical reassessment Methanol synthesis from CO2 hydrogenation with a Cu/Zn/Al/Zr fibrous catalyst Concurrent Production of Methanol and Dimethyl Ether from Carbon Dioxide Hydrogenation: Investigation of Reaction Conditions The National Science Foundation (NSF-MRI, CBET 0821370), R. Welch Foundation (AC-0006) from the Texas A&M University-Kingsville, and Texas A&M Energy Institute are duly acknowledged for their financial support.