Advancing Sustainable Green Shipping: Advancing sustainable green shipping by carbon capture, utilization, and storage through simulation technologies.

Limits to Paris compatibility of CO2 capture and utilization

Will blue hydrogen lock us into fossil fuels forever?

Carbon dioxide (CO2) emitted into the atmosphere by fossil fuel combustion is the most significant greenhouse gas contributing to climate change. Use of coal alone accounts for 43% of global CO2 emission in 2010. As the most abundant, the most reliable and cheap energy source, coal will continue to play a significant role in the world’s economy and improving people’s standard of living in particular in the developing countries. With the strong demand for coal, there is no doubt that the CO2 emissions will continue to rise. On May 9, 2013, the daily mean concentration of carbon dioxide in the atmosphere of Mauna Loa, Hawaii, surpassed 400 ppm for the first time since measurements began in 1958. The rate of increase is ca 2.1 ppm per year during the last 10 years. Without significant reduction of CO2 emissions, it is unlikely to limit the long-term concentration of greenhouse gasses to 450 ppm CO2 by 2050. Carbon capture and storage (CCS) is a process CO2 is separated from large point sources, including fossil fuel power plants, and transported to a disposal site, normally an underground geological formation, for permanent storage. It is generally agreed that CCS is the only technology available to make deep cuts in greenhouse gas emissions while still using fossil fuels and much of today’s energy infrastructure. According to the International Energy Agency (IEA), CCS will account for 19% of total emissions reduction if the global CO2 emissions are halved by 2050. However, looking back, there has been great uncertainty surrounding the commercial implementation of CCS technologies. Despite the fact that all the necessary components of CCS process are commercially available, the question about the large scale CO2 storage remains. The progress towards the commercial deployment of CCS technologies is slow. A number of factors contribute to a slow progress of CCS development. Firstly, the CCS projects are very costly. Most studies estimate that CCS will add more than 50% to the cost of electricity from coal. The costs for the first commercial CCS plants will be much higher than the following projects. No one wants to take the risk to be the first one. Secondly, CCS depends on the political polices to drive it. There is no a legally binding agreement on the emissions reduction applied to all countries and there is no market for CCS. Last but not the least, CCS depends on the government support. In an unfavourably financial environment, the R & D spending is expected to decline. Recently Australian government has announced a budget cut of $500 million over three years to its national CCS flagship program, almost one third of the total funding from the federal government. The Australia’s opposition party has even pledged to abolish the carbon tax if elected in September 2013. So, what is the future for CCS? It is a difficult question to answer. A critical issue is who is going to pay for the development of CCS. It should be pointed out that the majority of the upcoming projects use captured CO2 for enhanced oil recovery. The reason for that is EOR can facilitate the development of CCS by improving the financial viability of the CCS, building the infrastructure required for CCS, and developing capability along the supply chain. An increase in EOR projects reflexes the importance of CO2 utilisation. Carbon Capture, Utilisation and Storage (CCUS) is gaining increased attention in particular in USA and China. It is unlikely for the developing counties to deploy the CCS technologies with financial support from the government alone. In these countries the priorities are to sustain the economic growth and improve people’s living standard. To move CCS forward, it is important to realise the challenges facing the CCS development and make appropriate adjustment based on the political and economic realities. Considering that the funding on the development of CCS is limited, the international R & D program needs to be well coordinated and have the right focus and the right scale to avoid unproductive overlap between demonstration projects and ensure that limited resources are spent wisely to achieve the highest benefits. As a researcher working on CO2 capture, I am glad to

Qatar is the biggest exporter of liquefied natural gas, LNG, in the world and is a main oil-producing member of The Organization of Petroleum Exporting Countries, OPEC. A fossil fuel-based industry emerged around the ports of Ras Laffan and Mesaieed, Qatar's industrial cities, perusing industrial diversity and maximising the huge fossil fuel reserves that serve as the primary feedstock for the industrial sector. LNG, crude oil, and petroleum products has given Qatar a per capita GDP that ranks among the highest in the world with the lowest unemployment. This also has given Qatar a per capita CO 2 emissions among the highest in the world. A recent report from The World Health Organisation, stated that the capital of Qatar, Doha, is one of the world's most polluted cities and its air ranked the 12th highest average levels of small and fine particles which are particularly dangerous to health [1]. The people and wise leadership of Qatar recognizes the significance of the problem and made environmental development one of the four pillars of Qatar National Vision 2030. The vision places environmental preservation for Qatar's future generations at the forefront. Qatar Carbonates and Carbon Storage Research Centre is an example demonstrating Qatar's commitment to preserve the envioronment by investigating and implementing key technologies such as carbon capture and storage (CCS) to address the next step in climate change. CCS in deep saline aquifers is an important process for CO 2 reduction on industrial scales. The aim of CCS is to safely sequester CO 2 generated from stationary sources, such as power-plants, into aquifers and depleted oil reservoirs. It is considered a valuable option to reduce greenhouse gases and has been proposed as a practical technology to tackle climate change [2–4]. The importance of CCS as a key option to mitigate CO 2 emissions and combat climate change has been highlighted also in a report by the International Energy Agency (IEA) and suggests that CCS could contribute to a 17% reduction in global CO 2 emissions by 2035 [5]. Previously, carbon dioxide injection into the subsurface has mainly been used for enhanced oil recovery (EOR) purposes. That gave rise to Carbon capture, utilization and storage (CCUS) processes in mature oil reservoirs where CO 2 is first used to enhance oil recovery and then ultimately stored in the reservoir. The incremental hydrocarbon recoveries associated with CCUS make it more attractive to implement compared to CCS. It have significant energy, economic and environmental benefits and is considered an important component in achieving the widespread commercial deployment of CCS technology. Residual trapping of CO 2 through capillary forces within the pore space of the reservoir is one of the most significant mechanisms for storage security and is also a factor determining the ultimate extent of CO 2 migration within the reservoir. Observations and modelling have shown how capillary, or residual, trapping leads to the immobilisation of CO 2 in saline aquifer reservoirs, limiting the extent of plume migration, enhancing the security and capacity of CO 2 storage [6,7]. In contrast, carbonate hydrocarbon reservoirs are characterised by a mixed-wet state in which the capillary trapping of nonpolar fluids have been observed to be significantly reduced relative to trapping in rocks typical of saline aquifers unaltered by the presence of hydrocarbons [8,9]. There are, however, no observations characterising the extent of capillary trapping that will take place with CO 2 in mixed-wet carbonate rocks, the same rock type found in Qatar's subsurface geological formations and many other giant oil reservoirs in the Middle East that hold most of the oil in the world [10, 11]. Experimental tests of CO 2 and brine in carbonate rocks at reservoir conditions are very challenging due to the complex and reactive nature of carbonates when dealing with corrosive fluids pair of CO 2 and brine. In this study, we compare residual trapping efficiency in water-wet and mixed-wet carbonates systems on the same rock sample before and after wettability alteration by aging with oil mixture of Arabian medium crude oil. The experimental work was conducted using a state of the art multi-scale imaging laboratory (core and pore scale) developed at Imperial College London designed to characterise reactive transport and multiphase flow, with and without chemical reaction for CO 2 -brine systems in both sandstone and carbonate rocks at reservoir conditions [12]. The flow loop included stir reactor to equilibrate rock with fluids, high precision pumps, temperature control, the ability to recirculate fluids for weeks at a time and an x-ray CT scanner and micro x-ray scanner for in situ saturation monitoring. The wetted parts of the flow-loop are made of anti-corrosive material that can handle co-circulation of CO 2 and brine at reservoir conditions with the ability to preserve the rock sample from reacting to carbonic acid. We report the initial-residual CO 2 saturation curve and the resulting parameterisation of hysteresis models for both water-wet and mixed-wet systems. A novel core-flooding approach was used, making use of the capillary end effect to create a large range in initial CO 2 saturation in a single core-flood. Upon subsequent flooding with CO 2 -equilibriated brine, the observation of residual saturation corresponded to the wide range of initial saturations before flooding resulting in a rapid construction of the initial residual curve. Observations were made on a single Estaillades limestone core sample. It was made first on its original water-wet state, then were measured again after altering the wetting properties to a mixed-wet system. In particular, CO 2 trapping was characterized before and after wetting alteration so that the impact of the wetting state of the rock is observed directly on both core and pore scales. A carefully designed wettability alteration programme was designed in this study to replicate a mixed-wet carbonate system similar to those found in Qatari oil reservoirs. At the pore level, oil can precipitate asphaltene and other heavy components after long exposure with the rock changing the wetting state of the surface to oil-wet. A mixture of the evacuated crude oil with an organic precipitant, n-heptane, was used to deposit a stable oil-wet film. The precipitant substituted some of the evaporated and oxidised light hydrocarbon originally existed in the crude and deposited asphaltene to generate a stable strongly oil-wet film layer. Filtration experiments were carried out to sensibly precipitate enough asphaltene for a stable and strong oil-wet film without over precipitating and causing fine migration that can damage the core sample. The weight fraction of asphaltene precipitated with different fractions of crude-precipitant mixtures were measured. The diluent consisted of toluene as the solvent and heptane as the precipitant. 40 ml of the diluent was thoroughly mixed with 1 ml of Arabian Medium crude oil at 11 different precipitant/solvent volume ratios ranging from 0–100% at 10% increments and then left in the dark for 48 hours to allow the system to come to equilibrium. The mass of precipitated asphaltenes was measured in each mixture by vacuum filtration using a 0.45 micron polytetrafluoroethylene hydrophobic filter paper (Millipore) and evaporation of any remaining liquid oil from the filter paper. No asphaltene was precipitated at low precipitant volume fraction and only above the onset of precipitation, a linear relationship was seen between the wt% precipitated asphaltenes and the volume % of the precipitant in the mixture. The onset for asphaltene precipitation for an oil mixture of Arabian Medium crude oil and heptane alone without solvent was calculated at the onset using the volume fractions of the components with the mixing rule. The sample's wettability was altered to a mixed-wet using the appropriate oil mixture as measured using the filtration test and the oil was then removed from the sample by CO 2 enhanced oil recovery injected above the minimum miscibility pressure. This allowed for producing unique dataset and a great complement to the more theoretical analysis. That is if we make a surface oil-wet (to water), how does it behave in the presence of a gas. Here we show that residual CO 2 trapping in mixed-wet carbonate rocks characteristic of hydrocarbon reservoirs is significantly less than trapping in water-wet systems characteristic of saline aquifers. We found that in the native water-wet state of the carbonate sample, the extent of trapping of CO 2 and N 2 were indistinguishable, consistent with past studies of trapping and multiphase flow properties in water-wet sandstones [13, 14]. After alteration of the wetting state of the same rock sample with oil, the residual trapping of N 2 was reduced compared to the amount in the pre-altered rock. Surprisingly, the trapping of CO 2 was reduced even further. The unique results were complemented with pore scale observations to investigate the balance of interfacial tensions and contact angles in three-phase flow. Our results show that one of the key processes for maximising CO 2 storage capacity and security is significantly weakened in hydrocarbon reservoirs relative to saline aquifers. We anticipate this work to highlight a key issue for the early deployment of carbon storage – that

Carbon capture and storage (CCS) is one of the provisional technologies to mitigate the rise of greenhouse gases emission which comes from carbon dioxide (CO2) emission. The growth and development of CCS technology leads to existence of carbon capture, utilization and storage (CCUS) technologies due to immature technologies of CO2 storage. Criticality of carbon reduction attracts researchers to study the efficiency of implementing CCS and CCUS latest technologies with economic and environmental goals. This paper discusses the overview of the technologies and the work done by researchers on strategies of implementation of CCS and CCUS. This paper also focuses on the optimal planning of CCS and CCUS technologies. A new framework for carbon reduction, capture, utilization and storage (CARSUS) is introduced for future development. CARCUS is expected to present the best route for carbon dioxide avoidance.

The carbon capture, utilization and storage (hereinafter referred to as “CCUS”) technology has already been widely regarded as an available method of great potential for carbon dioxide emission reduction. As predicted, the emission reduction contribution will rise from 3% of the total emission reduction amount in 2020 to 10% in 2030, and to about 20% in 2050, which becomes the individual technology of the greatest contribution to the carbon dioxide emission reduction. This paper illustrates the main links of CCUS technology: the carbon capture process, carbon transport, carbon utilization and carbon storage. This paper introduces the storage methods of carbon dioxide, the geological storage and marine storage. In addition, this paper also analyzes the main storage practices both at home and abroad, the major overseas storage projects and the present status and progress of China’s storage. In addition, this paper also discusses the main challenges encountered by China’s CCUS development, and proposes the ideas and policy suggestions that promote China’s CCUS development.

Net-zero emissions chemical industry in a world of limited resources

Carbon Capture and Storage (CCS) euphoria is turning the oil and gas operations upside down, without having any perceptible impact on atmospheric carbon dioxide (CO2) that continues to increase. It is intended to show that the current CCS regimen has serious technical and fiscal constraints, and questionable validity. Carbon Capture, Storage, and Utilization (CCUS) is also discussed briefly. There is ample data to show that the CO2 concentration in the atmosphere is unrelentingly increasing, and the annual global CCS is about 0.1% of the 40 billion tonnes emitted. As much as 30% of the carbon dioxide captured is injected/re-injected into oil reservoirs for oil production and is not CCS at all. Several CCS methods are being tested, and some are implemented in dedicated plants in the world. A number of impediments to CO2 capture are identified and limited remedies are offered. It is shown that the problem is so gigantic and has so many dimensions that limited solutions have little efficacy. For example, about one-half of the world's population lives at less than $5 a day and has no recourse to CCS technologies. Major facets of the CCS problem are: (1) Validity of the future atmospheric CO2 concentrations based on the 100+ climate models for global warming. This is not the main discussion but is touched upon. (2) Impact of the desired CO2 concentrations on coal, oil, and gas production. (3) Principal CCS methodologies, including Direct Air Capture. (4) CCS vis-à-vis carbon tax, carbon credits, and carbon trading. (5) CCS subsidies – Is CSS workable without subsidies? At this time, No. The current tax credits for CCUS do not make sense. Finally, attention is given to CCS on a world scale – showing that so long as the great disparities in the living standards exist, CCS cannot be achieved to any significant level. All of the above is seen against the backdrop of oil and gas production and achieving Net Zero. It is shown that globally CCS has not increased beyond ∼0.1% of the global CO2 emissions in the past 20 years. The problem is that in CCS, there is injection only, no production! The paper offers partial solutions and concludes that oil and gas will continue to be energy sources far beyond the foreseeable future, and oil companies will accomplish the needed CSS.

Open AccessCCS ChemistryMINI REVIEWS28 Dec 2022Electrocatalytic CO2 Reduction over Bimetallic Bi-Based Catalysts: A Review Wei Chen, Yating Wang, Yuhang Li and Chunzhong Li Wei Chen Key Laboratory for Ultrafine Materials of Ministry of Education, Shanghai Engineering Research Center of Hierarchical Nanomaterials, Frontiers Science Center for Materiobiology and Dynamic Chemistry, School of Materials Science and Engineering, East China University of Science and Technology, Shanghai 200237 , Yating Wang Key Laboratory for Ultrafine Materials of Ministry of Education, Shanghai Engineering Research Center of Hierarchical Nanomaterials, Frontiers Science Center for Materiobiology and Dynamic Chemistry, School of Materials Science and Engineering, East China University of Science and Technology, Shanghai 200237 , Yuhang Li *Corresponding authors: E-mail Address: [email protected] E-mail Address: [email protected] Key Laboratory for Ultrafine Materials of Ministry of Education, Shanghai Engineering Research Center of Hierarchical Nanomaterials, Frontiers Science Center for Materiobiology and Dynamic Chemistry, School of Materials Science and Engineering, East China University of Science and Technology, Shanghai 200237 and Chunzhong Li *Corresponding authors: E-mail Address: [email protected] E-mail Address: [email protected] Key Laboratory for Ultrafine Materials of Ministry of Education, Shanghai Engineering Research Center of Hierarchical Nanomaterials, Frontiers Science Center for Materiobiology and Dynamic Chemistry, School of Materials Science and Engineering, East China University of Science and Technology, Shanghai 200237 School of Chemical Engineering, East China University of Science and Technology, Shanghai 200237 https://doi.org/10.31635/ccschem.022.202202357 SectionsAboutAbstractPDF ToolsAdd to favoritesDownload CitationsTrack Citations ShareFacebookTwitterLinked InEmail Electrocatalytic reduction of carbon dioxide (CO2) to valuable fuels is an up-and-coming approach. Owing to the low cost, environmental friendliness, and high selectivity to formate single product at low overpotentials, bismuth (Bi)-based catalysts have attracted extensive research attention. In this review, the reaction mechanisms of Bi-based catalysts are first introduced, and the bimetallic Bi-based catalysts synthesized by alloying, doping, and loading strategies are reviewed from the aspects of catalyst component, morphology, synthesis procedure, and performance optimization for electrocatalytic CO2 reduction. We provide an in-depth discussion of the existing challenges and an outlook for this highly promising kind of electrocatalysis. Download figure Download PowerPoint Introduction The energy crisis and environmental pollution have been ongoing significant issues and the focus of the international community. Over the past few decades, the strong dependence and overuse of fossil fuels has resulted in a rapid increase in the concentration of carbon dioxide (CO2) in the atmosphere.1,2 When the World Meteorological Organization released its latest Greenhouse Gas Bulletin, they pointed out that the current CO2 concentration in the atmosphere is 149% of preindustrial levels.3 The Bulletin additionally noted that greenhouse gases have increased by 47% through radiative forcing, with CO2 accounting for 80% of this increase from 1990 to 2020. The emission of an oversized quantity of CO2 and other harmful gases has resulted in global warming and environmental pollution, documented in numerous studies related to the energy and environment around the world. CO2 emission reduction is urgently needed. Electrocatalytic CO2 reduction reaction In order to curtail the global warming trend, scientists conduct in-depth discussions and research on the issue of reducing CO2 emissions. There are four primary strategies: (a) developing new clean energy technologies; (b) upgrading existing processes to eliminate and replace the low-efficiency sectors and equipment in traditional technologies;1 (c) afforestation and forestation; and (d) carbon capture, utilization and storage.4,5 Research on carbon capture, carbon storage, and carbon utilization has produced many advances and breakthroughs in CO2 storage and conversion. Among them, carbon capture and storage technology have certain limitations. First of all, the technology is expensive. Second, storage equipment may leak and cause a series of other hidden safety problems, such as local seawater acidification. In contrast, carbon capture and utilization technology, which reduce CO2 and convert it into usable chemical value-added fuels, possesses greater development prospects.6–8 Not only can this technology reduce high CO2 concentrations in the atmosphere, but it also produces renewable fuels to combat the energy crisis. In recent years, numerous catalytic conversion methods have been developed successively. The methods used for CO2 reduction chiefly include biological (enzyme) catalysis, photocatalysis, thermocatalysis, and electrocatalysis.9–12 At present, electrocatalysis as an emerging energy technology for CO2 emission reduction and production of value-added fuels receives a great deal of research attention.7 Compared with traditional industrial processes, electrocatalytic CO2 reduction reaction (CO2RR) can be carried out under milder environmental conditions, improving electrochemical stability and selectivity in CO2RR via selecting appropriate electrocatalysts to manipulate reaction-tailored products.13 In this regard, reports in the literature demonstrate the exploration of various electrocatalysts and electrode reaction mechanisms for CO2RR. CO2RR also utilizes renewable energy for catalytic reactions to achieve large-scale energy storage and production of high-energy products.14 Generally, CO2RR is in a position to produce a variety of reduction products through electrocatalysis. The corresponding reduction products are different as electron-transferred numbers change. Electrocatalytic CO2RR products are categorized as formic acid (HCOOH),12 carbon monoxide (CO), methane (CH4), methanol (CH3OH) as C1, and ethanoic acid (CH3COOH), ethanol (C2H5OH)15 as C2.16,17 The above reduction products are obtained by various electron-transfer mechanisms and half-reactions, as shown in Table 1.18,19 Table 1 | Electrochemical Potentials of Several CO2 Reduction Reactions CO2 Reduction Half-Reactions Electrode PotentialV (vs SHE) Electrode PotentialV (vs RHE) CO2 + 2H+ + 2e− → CO + H2O −0.52 −0.106 CO2 + 2H+ + 2e− → HCOOH −0.61 −0.250 CO2 + 4H+ + 4e− → HCHO + H2O −0.51 −0.070 CO2 + 6H+ + 6e− → CH3OH + H2O −0.38 0.016 CO2 + 8H+ + 8e− → CH4 + 2H2O −0.24 0.169 2CO2 + 12H+ + 12e− → C2H4 + 4H2O −0.34 0.064 2CO2 + 12H+ + 12e− → C2H5OH + 3H2O −0.33 0.084 During the electrocatalytic reduction process, not solely CO2RR but also other side reactions will occur, resulting in the complexity of the reaction. For instance, the hydrogen evolution reaction (HER) competes with CO2RR to generate H2, which decreases the performance of CO2RR20–22 in order to efficiently overcome the energy barrier of electron-transfer proton coupling, accelerate the catalytic reaction rate. and suppress the occurrence of side reaction processes. The development of ideal catalysts with remarkable CO2RR selectivity and activity is the focus of current research. Several parameters of electrocatalytic performance for CO2RR catalysts can primarily be evaluated, including Faradaic efficiency (FE), overpotential, current density, Tafel slope, stability, and so on.7,12,14 FE is the charge required as a percentage of the initial charge to cross the working electrode and facilitate the electrochemical reaction. In simple terms, FE is a significant indicator to measure the selectivity of electrocatalytic CO2RR products.23 Due to the complex reaction mechanism and sluggish kinetics, the actual reduction reaction working potential is more negative than the theoretical reduction potential. High reduction overpotentials lead to wasted energy and significant HER reactions. Therefore, overpotential is an important indicator in evaluating the electrocatalytic activity of CO2RR catalysts. Studies confirm that when current density goes above 300 mA cm−2, the production cost will be reduced as much as possible.24 The equation of Tafel (η = blgj + a) is able to directly reflect the rate of reaction dominated by kinetics. The smaller the Tafel slope of b in the equation, the faster the electrochemical reaction rate and the higher the catalytic activity, which is more favorable for the electrocatalytic reaction.25 Stability is an indicator of whether an excellent electrocatalyst possesses long-term stability and efficiency.26 The stability of electrocatalysts is usually effectively assessed with potentiostatic electrolysis or cyclic voltammetry. Bismuth-based electrocatalysts Recently, P-block electrocatalysts consisting of bismuth (Bi),27–30 tin (Sn),31–33 lead (Pb),34–36 and indium (In)37,38 have inarguably facilitated electrocatalytic CO2 reduction with remarkable selectivity for C1 products, especially formic acid or formate. The advantage of electrocatalytic generation of formate lies in the high selectivity and current density achieved by prohibiting competing side reactions. Compared with other value-added products from CO2 reduction, which are difficult to solely generate and low in yield, the FE of Bi-based CO2 toward formate can reach nearly 100%.39 In addition, formate is a liquid product with excellent chemical stability at room temperature for storage and transportation compared to gas-phase products such as CO. Experts evaluate various chemicals with economic viability in CO2RR and discovered that formate has considerable marketability.13 Moreover, converting CO2 toward formate is a 2-electron transfer process, leading to a low production cost of 1$US/0.59 kg, suggesting that CO2 electrolysis of formate is more cost-competitive than the C2 product production process.40 It may be difficult to attain widespread application of Pb and In metals on a marketable scale because of toxicity or low availability. However, Bi is a dramatic and promising electrocatalyst due to its low cost, nontoxicity, environmental safety, relatively single reduction product, and high formate generation activity. Bi-based catalysts can be traced back to the Bi electrocatalyst synthesized by Komatsu's team in 1995.41 In the following decades, research on Bi-based catalysts continued to deepen. Monometallic catalysts, including metallic Bi, are currently a hot topic in the field of electrocatalysis. Recently, with in-depth exploration and development of synthesis techniques, various nanostructured monometallic Bi catalysts have been designed, such as nanoparticles, nanowires, nanotubes, nanosheets, nanodendrites, and so on, in multidimensional aspects. However, monometallic Bi catalysts may be undesirable for the breakthrough of formate electrosynthesis, owing to the limited active sites on the catalyst surface. This means that monometallic Bi catalysts usually require high overpotential to achieve high formate FE and partial current density. Compared with the monometallic Bi catalysts that use advanced synthetic strategies or tedious structural optimization to enhance their performance, bimetallic Bi-based catalysts will further involve synergistic effects. The synergistic interaction between bimetals gives the bimetallic electrocatalyst a superior catalytic performance.42 The synergistic effects in bimetallic Bi-based catalysts can be broadly viewed as Bi acting as the active site and the other metals mainly playing three roles: (1) tailoring the electronic structures of Bi sites, (2) regulating the adsorption states of the key intermediates, and (3) generating interfacial active sites to further enhance performance. Through the electronic structure modulations by the second metal, the bimetallic Bi-based catalysts will boost the formation of the key intermediate OCHO*, thus improving the performance of CO2 electroreduction to formate. The activity, selectivity, and stability will be further improved via preparing bimetallic Bi-based materials through strategies such as alloying, surface doping, defect introduction, and nanoengineering. Here, in this review, the representative reaction pathways of Bi-based electrocatalysts are first introduced, and then the reaction mechanisms of bimetallic Bi-based heterogeneous CO2RR electrocatalysts are summarized with examples from the perspective of reaction pathways. Afterward, based on the Bi-based electrocatalysts in recent development, we divide bimetallic Bi-based catalysts into three categories: (1) alloyed Bi, (2) doped Bi, and (3) supported Bi. For each category, we describe in detail its performance-enhancing strategies and provide examples of catalysts, including descriptions of their preparation process, composition, morphology, catalytic activity, and product properties. Finally, we provide an in-depth analysis of the existing challenges and the current outlook for this field. Reaction Mechanisms of the Bi-Based Electrocatalysts Bi-based catalysts have high efficiency, selectivity, and stability to form formate via electrocatalytic CO2RR in aqueous solutions. They also possess the capacity to generate CO, according to some reports.43 The pathways of the formate and CO products are comparatively simple compared to that of other CO2RR products, and the essential difference is the intermediate products. An in-depth study of the electrocatalytic CO2RR process on the surface of Bi-based catalysts is required for a good understanding of the catalytic mechanism of Bi metals. In general, there are three types of steps involving the generation of products theoretically, consisting of: (1) reactant adsorption on the electrocatalytic surface, (2) transfer of electrons and protons to the reactant, and (3) the products desorption from the electrocatalyst surface.44 Research demonstrates that the first proton coupling determines the selectivity for a catalyst, which takes place at the C or O in CO2*− radical anion. Three reaction pathways for electrocatalytic CO2RR over Bi-based catalysts are displayed in Figure 1: (a) Generally, CO2 comes into contact with the catalyst via carbon or oxygen atoms. If the carbon atom binds to the catalyst electrode surface first, *COOH intermediate will be formed, which is the first intermediate for CO2 activation in this pathway. However, *COOH intermediate will have multiple pathways in the second proton coupling electron transfer (PCET) process, which is not conducive to promoting highly selective formate production. *COOH can lose H2O to form CO, or be reduced to form HCOOH. (b) Compared to pathway a, pathway b is different in that the oxygen is bound to the electrode surface, by which CO2* − hydrogenation forms the HCOO* intermediate.19 Based on the reaction mechanism of Bi-based catalysts, the second PCET process of the HCOO* intermediate can only generate HCOOH.(c) In the pathway c, CO2 forms the OCHO* intermediate during the first PCET when only one oxygen molecule is bound to the surface electrode. Formate is the only product obtained via a subsequent second PCET process. Theoretical analyses indicate that the formation energy barrier of OCHO* intermediate is lower than that of *COOH and HCOO* intermediates, leading to the importance of OCHO* intermediates in the Bi-based electroreduction process.45 Figure 1 | Possible electrochemical reaction pathways of CO2 over Bi-based catalysts. Download figure Download PowerPoint Theoretical calculations confirm that the CO2RR process of Bi-based catalysts follows the key intermediate of OCHO* from a PCET mechanism, facilitating highly selective formate production. The specific mechanism equations (1–5) for reducing CO2 pathway in solution to HCOOH are summarized as follows:46 CO 2 ( g ) → CO 2 * (1) CO 2 * + e − → CO 2 * − (2) CO 2 * − + e − + H + → OCHO * − (3) OCHO * − + e − + H + → HCOOH * (4) HCOOH * → HCOOH ( aq ) + * (5)where * denotes the catalytic surface or adsorption site, initially the CO2 molecules are dissolved in the solution and contact the electrode surface to form adsorbed CO2*. Afterwards, single electron is transferred to CO2* that forms the CO2* − radical anion. According to HCO3 − ↔ H+ + CO32−, electron transfer and proton coupling form OCHO* − intermediates. Ultimately, OCHO* − forms formic acid solution by PCET. Since the slow kinetics of the electrocatalytic CO2RR process, HER side reactions inevitably generate H2, and some reduction reactions are accompanied by CO generation, which negatively affects the highly selective production of formate from Bi-based materials. For the purpose of obtaining more formate, the production of H2 and CO is reduced as much as possible. The catalytic mechanism may be diametrically different in the same Bi-based alloy, depending on the content of two metal elements. Therefore, the reaction mechanism is manipulated via controlling different proportions of the two metals in bimetallic Bi-based electrocatalysts. For instance, Zhang et al.47 have developed CuO/Bi(OH)3 decorated on carbon nanotubes for CO2 electroreduction. CuBi#8 and CuBi#4 are bimetallic nanoparticles obtained via a two-step hydrolysis method and adjusted the Cu/Bi ratio. CuBi#8 and CuBi#4 exhibit CO and formate FE of 96% and 60% at −0.99 V versus reversible hydrogen electrode (RHE) (VRHE), respectively. It is found that with Bi content increasing, HER is well suppressed, and the products are mainly CO. By further increasing Bi content, FEHCOOH rapidly increases accompanied by the rapid decrease of FECO. FEHCOOH reaches the maximum of 96% at 12.5 mA cm−2. The conversion of intermediates from *COOH to OCHO* via increasing Bi content further illustrates the high selectivity of OCHO* to formate. Adjusting the optimal Cu/Bi ratio suppresses the production of CO and H2, leading to efficient production of formate. In addition, defects such as oxygen vacancies or doped atoms significantly improve the catalytic performance.12 Li et al.48 have prepared Sn atom-doped Bi2O3 nanosheet (NS) electrocatalysts by constant electrolysis. Three products can be detected during the electrolysis, including H2, CO, and HCOOH. The Sn-doped Bi2O3 NSs current density is significantly increased compared to the undoped Bi2O3 NSs. The 2.5% Sn-doped Bi2O3 NSs exhibit high selectivity for formate, obtaining a supreme FE of 93.4% at the potential of −0.97 V. The HER inhibition effect is significantly enhanced compared to the undoped Bi2O3 NSs. Moreover, the catalytic capacity is optimized by coping with significant HER and expanding its specific surface area. For the first time, metallic aerogel is a three-dimensional (3D) material that has attracted enormous attention due to its abundant specific surface area, contributing to the generation of more catalytic centers.49 In addition, adjusting the partial pH can also improve the selectivity of CO2RR, and proper control of pH into acidity facilitates the formation of formate.50 Advanced Bi-Based Electrocatalysts for CO2 Reduction In recent decades, various Bi-based CO2 reduction electrocatalysts have been exhaustively studied, mainly with formate as the end product. Especially, the preparation of bimetallic catalysts via different synthetic methods is the focus of most current studies. Bimetallic Bi-based catalysts can mainly be classified into three types: (1) alloyed Bi, (2) doped Bi, and (3) supported Bi. Detailed CO2RR performances of bimetallic Bi-based electrocatalysts are summarized in Table 2. Table 2 | Performance of Bimetallic Bi-Based Catalysts in Electrocatalytic CO2RR Catalyst Electrolyte Major Products FE (%) Potential at FEMax (V) Current Density (mA cm−2) Stability (h) References Bi5Sn60 0.1 M KHCO3 Formate 94.8 −1.0 (vs RHE) 34 20 52 BixSny/Cu 0.1 M KHCO3 Formate 90.4 −0.84 (vs RHE) 30 12 53 Bi-Sn aerogel 0.1 M KHCO3 Formate 93.9 −1.0 (vs RHE) 9.3 10 57 Cu-Bi 0.1 M KHCO3 Formate 90 −0.8 (vs RHE) >2 — 60 CuBi-100 0.5 M KHCO3 Formate 94.7 −1.0 (vs RHE) 12.8 8 61 CuBi 0.5 M KHCO3 Formate 94.4 −0.97 (vs RHE) 38.5 — 62 CuBi 0.5 M KHCO3 Formate 98.3 −1.07 (vs RHE) 56.6 — 62 Bi/Cu 0.5 M KHCO3 Formate 95 −0.9 (vs RHE) 59.7 12 64 CuBi75 0.5 M KHCO3 Formate 100 −0.77 (vs RHE) 33.65 24 66 Cu1-Bi/Bi2O3@C 0.5 M KHCO3 Formate 93.4 −0.94 (vs RHE) 10.1 10 67 Pd3Bi-IMA 0.1 M KHCO3 Formate >90 −0.35 (vs RHE) 3 8 68 a-NPSB 0.1 M KHCO3 Formate 88.4 −1.15 (vs RHE) 21.2 18 70 Bi–Pt complex 0.1 M TBAPF6/THF CO 82 −1.25 (vs NHE) 0.125 — 71 Mo-Bi BMC/CP 0.5 M [Bmim]BF4 CH3OH 71.2 −0.7 (vs SHE) 12.1 — 72 Sn-doped Bi2O3 NSs 0.5 M KHCO3 Formate 93.4 −0.97 (vs RHE) 24.3 8 48 Bi/Bi(Sn)Ox NWs 1 M KOH Formate ∼100 −0.7 (vs RHE) 301.4 20 77 Cu-Bi2Se3 0.5 M NaHCO3 Formate 65.31 −1.3 (vs RHE) 24.1 24 78 Ce–[email protected]x/C 0.5 M KHCO3 Formate 96 −1.7 (vs SHE) 15.2 10 79 BiIn5[email protected] 0.5 M KHCO3 Formate 97.5 −0.86 (vs RHE) 13.5 15 81 Bi-Sn/CF 0.5 M KHCO3 Formate 96 −1.1 (vs RHE) 45 100 82 Sn0.80Bi0.20@Bi-SnOx 0.5 M KHCO3 Formate 95.8 −0.88 (vs RHE) 74.6 — 83 Bi-SnO/Cu 0.1 M KHCO3 Formate 93 −1.7 (vs Ag/AgCl) — 30 84 [email protected] 0.5 M NaHCO3 Formate 95 (vs RHE) 15 12 45 NSs 0.5 M KHCO3 Formate −0.86 (vs RHE) 8 90 0.5 M KHCO3 Formate −0.8 (vs RHE) 0.5 M KHCO3 Formate −0.8 (vs RHE) 10 [email protected] 0.5 M KHCO3 Formate (vs RHE) 10 M Formate (vs RHE) 34 Bi The is one of the methods to enhance the electrocatalytic performance of Bi-based effects facilitate the catalytic reaction by a between two different metal elements. P-block catalysts have CO2 conversion that is highly selective for Among them, Bi-Sn bimetallic is the most is a and method for the preparation of The method a of two metallic elements. Bimetallic obtained via are or and possess such as high density and can improve the catalytic activity of the catalyst Li et have two Bi and on the an In this different electrode The at different of This structure is to the surface and more catalytic When the of metal Bi and the of metal Sn 60 the catalytic performance the as the of −1.0 with mA partial current density, the FE of formate it excellent formate yield, which superior to most electrocatalysts. The of bimetallic is to the OCHO* intermediate and suppress the HER process. Li et have also electrocatalysts on and discovered that the FE of formate enhanced by the Bi content in the BixSny/Cu electrode. is an emerging in electrocatalytic due to their structure and the of the catalyst, contributing to the generation of more catalytic Bimetallic prepared by the method it to compared with methods such as or solution et have prepared Bi-Sn bimetallic under with and abundant Bi and Sn the of via controlling the ratio. with with a electron as shown in Figure abundant of that favorable for and abundant active sites during electrocatalysis. The of the Bi-Sn aerogel well with of Sn and Bi suggesting that the obtained aerogel is a Bi-Sn The that the are and corresponding to the and of Bi and This that the Sn and Bi are and more reaction sites are during the catalytic process. The the of Sn and Bi in the The electrochemical performance displayed compared with Sn and Bi catalysts, Bi-Sn aerogel excellent performance for formate with FE as high as Density that electronic between Bi and Sn the energy barrier for formate, the electrocatalytic performance In can indicate the reaction pathway of Bi-Sn aerogel bimetallic catalyst in CO2RR. shown in Figure the at at V and more as the potential increased from to V. This is to the that in the formate intermediate HCOO* is in suggesting that the synergistic effects between Bi-Sn bimetals can the generation of Figure 2 | (a) of the synthesis of Bi-Sn (b) of (c) of (d) and the corresponding of the catalytic mechanism of the of Bi-Sn with various with from Download figure Download PowerPoint is a and catalyst in the field of electrocatalysis. The product selectivity of catalysts is C1 products such as formate and CH4 and value-added fuels such as The of the Bi and to form a Cu-Bi usually formate conversion and the HER The reaction intermediates with of the between bimetallic Cu-Bi facilitate the catalytic reaction. et have synthesized bimetallic Cu-Bi electrocatalysts with Owing to the difference between Bi and the of bimetallic defect sites with high density, leading to the formation of more catalytic Cu-Bi exhibit lower current for HER and CO evolution thus the higher selectivity of Cu-Bi for formate. At −0.8 the FE of the formate product In to materials obtained by have numerous and catalytic activity will be Through the of bimetallic catalysts, the of reaction sites of electrocatalysts are increased as much as and the electrochemical of product selectivity is For instance, et have synthesized bimetallic Cu-Bi electrocatalysts by at room temperature In the by the of CuBi-100 the electrochemical performance At the potential from −0.8 V to CuBi-100 excellent selectivity for formate and FE of more than The supreme at the potential of −1.0 electron that CuBi-100 on carbon and a The of CuBi-100 has

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