A general descriptor for guiding the electrolysis of CO_(2)in molten carbonate

Molten carbonate is an excellent electrolyte for the electrochemical reduction of CO_(2)to carbonaceous materials.However,the electrolyte–electrode-reaction relationship has not been well understood.Herein,we propose a general descriptor,the CO_(2)activity,to reveal the electrolyte–electrode-reaction relationship by thermodynamic calculations and experimental studies.Experimental studies agree well with theoretical predictions that both cations(Li^(+),Ca^(2+),Sr^(2+)and Ba^(2+))and anions(BO_(2)^(-),Ti_(5)O_(14)^(8-),SiO_(3)^(2-))can modulate the CO_(2)activity to control both cathode and anode reactions in a typical molten carbonate electrolyzer in terms of tuning reaction products and overpotentials.In this regard,the reduction of CO_(3)^(2-)can be interpreted as the direct reduction of CO_(2)generated from the dissociated CO_(3)^(2-),and the CO_(2)activity can be used as a general descriptor to predict the electrode reaction in molten carbonate.Overall,the CO_(2)activity descriptor unlocks the electrolyte–electrode-reaction relationship,thereby providing fundamental insights into guiding molten carbonate CO_(2)electrolysis.

Effect of CO_(2)exposure on the mechanical strength of geopolymerstabilized sandy soils

In recent years,there has been growing interest in developing methods for mitigating greenhouse effect,as greenhouse gas emissions continue to contribute to global temperature rise.On the other hand,investigating geopolymers as environmentally friendly binders to mitigate the greenhouse effect using soil stabilization has been widely conducted.However,the effect of CO_(2)exposure on the mechanical properties of geopolymer-stabilized soils is rarely reported.In this context,the effect of CO_(2)exposure on the mechanical and microstructural features of sandy soil stabilized with volcanic ash-based geopolymer was investigated.Several factors were concerned,for example the binder content,relative density,CO_(2)pressure,curing condition,curing time,and carbonate content.The results showed that the compressive strength of the stabilized sandy soil specimens with 20%volcanic ash increased from 3 MPa to 11 MPa.It was also observed that 100 kPa CO_(2)pressure was the optimal pressure for strength development among the other pressures.The mechanical strength showed a direct relationship with binder content and carbonate content.Additionally,in the ambient curing(AC)condition,the mechanical strength and carbonate content increased with the curing time.However,the required water for carbonation evaporated after 7 d of oven curing(OC)condition and as a result,the 14-d cured samples showed lower mechanical strength and carbonate content in comparison with 7-d cured samples.Moreover,the rate of strength development was higher in OC cured samples than AC cured samples until 7 d due to higher geopolymerization and carbonation rate.

Thermochemical splitting of CO_(2) on perovskites for CO production: A review

Energy supply dominated by fossil energy has been and remains the main cause of carbon dioxide emissions,the major greenhouse gas leading to the current grave climate change challenges.Many technical pathways have been proposed to address the challenges.Carbon capture and utilization(CCU) represents one of the approaches and thermochemical CO_(2) splitting driven by thermal energy is a subset of the CCU,which converts the captured CO_(2) into CO and makes it possible to achieve closed-loop carbon recirculation.Redox-active catalysts are among the most critical components of the thermochemical splitting cycles and perovskites are regarded as the most promising catalysts.Here we review the latest advancements in thermochemical cycles based on perovskites,covering thermodynamic principles,material modifications,reaction kinetics,oxygen pressure control,circular strategies,and demonstrations to provide a comprehensive overview of the topical area.Thermochemical cycles based on such materials require the consideration of trade-off between cost and efficiency,which is related to actual material used,operation mode,oxygen removal,and heat recovery.Lots of efforts have been made towards improving reaction rates,conversion efficiency and cycling stability,materials related research has been lacking-a key aspect affecting the performance across all above aspects.Double perovskites and composite perovskites arise recently as a potentially promising addition to material candidates.For such materials,more effective oxygen removal would be needed to enhance the overall efficiency,for which thermochemical or electrochemical oxygen pumps could contribute to efficient oxygen removal as well as serve as means for inert gas regeneration.The integration of thermochemical CO_(2) splitting process with downstream fuel production and other processes could reduce costs and increase efficiency of the technology.This represents one of the directions for the future research.

The photo-decomposition and self-restructuring dynamic equilibrium mechanism of Cu_(2)(OH)_(2)CO_(3)for stable photocatalytic CO_(2)reduction

Developing suitable photocatalysts and understanding their intrinsic catalytic mechanism remain key challenges in the pursuit of highly active,good selective,and long-term stable photocatalytic CO_(2)reduction(PCO_(2)R)systems.Herein,monoclinic Cu_(2)(OH)_(2)CO_(3)is firstly proven to be a new class of photocatalyst,which has excellent catalytic stability and selectivity for PCO_(2)R in the absence of any sacrificial agent and cocatalysts.Based on a Cu_(2)(OH)_(2)^(13)CO_(3)photocatalyst and 13CO_(2)two-sided^(13)C isotopic tracer strategy,and combined with in situ diffused reflectance infrared Fourier transform spectroscopy(DRIFTS)analysis and density functional theory(DFT)calculations,two main CO_(2)transformation routes,and the photo-decomposition and self-restructuring dynamic equilibrium mechanism of Cu_(2)(OH)_(2)CO_(3)are definitely revealed.The PCO_(2)R activity of Cu_(2)(OH)_(2)CO_(3)is comparable to some of state-of-the-art novel photocatalysts.Significantly,the PCO_(2)R properties can be further greatly enhanced by simply combining Cu_(2)(OH)_(2)CO_(3)with typical TiO_(2)to construct composites photocatalyst.The highest CO_(2)and CH_(4)production rates by 7.5 wt%Cu_(2)(OH)_(2)CO_(3)-TiO_(2)reach 16.4μmol g^(-1)h^(-1)and 116.0μmol g^(-1)h^(-1),respectively,which are even higher than that of some of PCO_(2)R systems containing sacrificial agents or precious metals modified photocatalysts.This work provides a better understanding for the PCO_(2)R mechanism at the atomic levels,and also indicates that basic carbonate photocatalysts have broad application potential in the future.

Porous metal oxides in the role of electrochemical CO_(2) reduction reaction

The global energy-related CO_(2) emissions have rapidly increased as the world economy heavily relied on fossil fuels.This paper explores the pressing challenge of CO_(2) emissions and highlights the role of porous metal oxide materials in the electrocatalytic reduction of CO_(2)(CO_(2)RR).The focus is on the development of robust and selective catalysts,particularly metal and metal-oxide-based materials.Porous metal oxides offer high surface area,enhancing the accessibility to active sites and improving reaction kinetics.The tunability of these materials allows for tailored catalytic behavior,targeting optimized reaction mechanisms for CO_(2)RR.The work also discusses the various synthesis strategies and identifies key structural and compositional features,addressing challenges like high overpotential,poor selectivity,and low stability.Based on these insights,we suggest avenues for future research on porous metal oxide materials for electrochemical CO_(2) reduction.

Elucidating the structure-activity relationship of Cu-Ag bimetallic catalysts for electrochemical CO_(2) reduction

Developing bimetallic catalysts is an effective strategy for enhancing the activity and selectivity of electrochemical CO_(2) reduction reactions,where understanding the structure-activity relationship is essential for catalyst design.Herein,we prepared two Cu-Ag bimetallic catalysts with Ag nanoparticles attached to the top or the bottom of Cu nanowires.When tested in a flow cell,the Cu-Ag catalyst with Ag nanoparticles on the bottom achieved a faradaic efficiency of 54%for ethylene production,much higher than the catalyst with Ag nanoparticles on the top.The catalysts were further studied in the H-cell and zero-gap MEA cell.It was found that placing the two metals in the intensified reaction zone is crucial to triggering the tandem reaction of bimetallic catalysts.Our work elucidates the structure-activity relationship of bimetallic catalysts for CO_(2) reduction and demonstrates the importance of considering both catalyst structures and cell characteristics to achieve high activity and selectivity.

Exploring the impact of Nafion modifier on electrocatalytic CO_(2) reduction over Cu catalyst

Nafion as a universal polymer ionomer was widely applied for nanocatalysts electrode preparation.However,the effect of Nafion on electrocatalytic performance was often overlooked,especially for CO_(2)electrolysis.Herein,the key roles of Nafion for CO_(2)RR were systematically studied on Cu nanoparticles(NPs)electrocatalyst.We found that Nafion modifier not only inhibit hydrogen evolution reaction(HER)by decreasing the accessibility of H_(2)O from electrolyte to Cu NPs,and increase the CO_(2)concentration at electrocatalyst interface for enhancing the CO_(2)mass transfer process,but also activate CO_(2)molecule by Lewis acid-base interaction between Nafion and CO_(2)to accelerate the formation of^(*)CO,which favor of C–C coupling for boosting C_(2)product generation.Owing to these features,the HER selectivity was suppressed from 40.6%to 16.8%on optimal Cu@Nafion electrode at-1.2 V versus reversible hydrogen electrode(RHE),and as high as 73.5%faradaic efficiencies(FEs)of C_(2)products were achieved at the same applied potential,which was 2.6 times higher than that on bare Cu electrode(~28.3%).In addition,Nafion also contributed to the long-term stability by hinder Cu NPs morphology reconstruction.Thus,this work provides insights into the impact of Nafion on electrocatalytic CO_(2)RR performance.

CO_(2)capture costs of chemical looping combustion of biomass:A comparison of natural and synthetic oxygen carrier

Chemical looping combustion has the potential to be an efficient and low-cost technology capable of contributing to the reduction of the atmospheric concentration of CO_(2) in order to reach the 1.5/2°C goal and mitigate climate change.In this process,a metal oxide is used as oxygen carrier in a dual fluidized bed to generate clean CO_(2) via combustion of biomass.Most commonly,natural ores or synthetic materials are used as oxygen carrier whereas both must meet special requirements for the conversion of solid fuels.Synthetic oxygen carriers are characterized by higher reactivity at the expense of higher costs versus the lower-cost natural ores.To determine the viability of both possibilities,a techno-economic comparison of a synthetic material based on manganese,iron,and copper to the natural ore ilmenite was conducted.The synthetic oxygen carrier was characterized and tested in a pilot plant,where high combustion efficiencies up to 98.4%and carbon capture rates up to 98.5%were reached.The techno-economic assessment resulted in CO_(2) capture costs of 75 and 40€/tCO_(2) for the synthetic and natural ore route respectively,whereas a sensitivity analysis showed the high impact of production costs and attrition rates of the synthetic material.The synthetic oxygen carrier could break even with the natural ore in case of lower production costs and attrition rates,which could be reached by adapting the production process and recycling material.By comparison to state-of-the-art technologies,it is demonstrated that both routes are viable and the capture cost of CO_(2) could be reduced by implementing the chemical looping combustion technology.

Cu/TiO_(2) Photocatalysts for CO_(2) Reduction: Structure and Evolution of the Cocatalyst Active Form

Extensive work on a Cu-modified TiO_(2) photocatalyst for CO_(2) reduction under visible light irradiation was conducted. The structure of the copper cocatalyst was established using UV-vis diff use refl ectance spectroscopy, high-resolution transmis- sion electron microscopy, X-ray absorption spectroscopy, and X-ray photoelectron spectroscopy. It was found that copper exists in different states (Cu 0 , Cu^(+) , and Cu^(2+) ), the content of which depends on the TiO_(2) calcination temperature and copper loading. The optimum composition of the cocatalyst has a photocatalyst based on TiO_(2) calcined at 700℃ and modified with 5 wt% copper, the activity of which is 22 μmol/(h·g cat ) (409 nm). Analysis of the photocatalysts after the photocatalytic reaction disclosed that the copper metal on the surface of the calcined TiO_(2) was gradually converted into Cu_(2) O during the photocatalytic reaction. Meanwhile, the metallic copper on the surface of the noncalcined TiO_(2) did not undergo any trans- formation during the reaction.

Experimental investigation of the effects of oil asphaltene content on CO_(2) foam stability in the presence of nanoparticles and sodium dodecyl sulfate

Foam stability tests were performed using sodium dodecyl sulfate(SDS)surfactant and SiO2 nanoparticles as foaming system at different asphaltene concentrations,and the half-life of CO_(2) foam was measured.The mechanism of foam stability reduction in the presence of asphaltene was analyzed by scanning electron microscope(SEM),UV adsorption spectrophotometric concentration measurement and Zeta potential measurement.When the mass ratio of synthetic oil to foam-formation suspension was 1:9 and the asphaltene mass fraction increased from 0 to 15%,the half-life of SDS-stabilized foams decreased from 751 s to 239 s,and the half-life of SDS/silica-stabilized foams decreased from 912 s to 298 s.When the mass ratio of synthetic oil to foam-formation suspension was 2:8 and the asphaltene mass fraction increased from 0 to 15%,the half-life of SDS-stabilized foams decreased from 526 s to 171 s,and the half-life of SDS/silica-stabilized foams decreased from 660 s to 205 s.In addition,due to asphaltene-SDS/silica interaction in the aqueous phase,the absolute value of Zeta potential decreases,and the surface charges of particles reduce,leading to the reduction of repulsive forces between two interfaces of thin liquid film,which in turn,damages the foam stability.

MOF基单原子催化剂用于CO_(2)还原的研究进展

CO_(2)资源化利用是实现“双碳”目标的重要途径之一。金属有机框架(metal-organic frameworks,MOF)材料具有高孔隙率、可调节的功能、丰富的活性位点和潜在锚定位点等优点;单原子催化剂(single-atom catalysts,SAC)有独特的电子结构和最大化金属利用率的优点。结合二者的优势,MOF基单原子催化剂在光/电催化CO_(2)还原反应中表现出良好的应用前景。系统地总结了MOF基单原子催化剂在光/电催化CO_(2)还原中的最新研究进展,主要分为2个部分:纯MOF固定的SAC和MOF衍生的SAC,分别探讨了各种制备策略和原理及在光/电催化CO_(2)还原中展现的独特优势,并从理化特性上分析了材料性能优势的成因。最后对以MOF基材料为光/电催化CO_(2)还原催化剂的研究进行了总结和展望。

Surface engineering of ZnO electrocatalyst by N doping towards electrochemical CO_(2) reduction

The discovery of efficient,selective,and stable electrocatalysts can be a key point to produce the largescale chemical fuels via electrochemical CO_(2) reduction(ECR).In this study,an earth-abundant and nontoxic ZnO-based electrocatalyst was developed for use in gas-diffusion electrodes(GDE),and the effect of nitrogen(N)doping on the ECR activity of ZnO electrocatalysts was investigated.Initially,a ZnO nanosheet was prepared via the hydrothermal method,and nitridation was performed at different times to control the N-doping content.With an increase in the N-doping content,the morphological properties of the nanosheet changed significantly,namely,the 2D nanosheets transformed into irregularly shaped nanoparticles.Furthermore,the ECR performance of Zn O electrocatalysts with different N-doping content was assessed in 1.0 M KHCO_(3) electrolyte using a gas-diffusion electrode-based ECR cell.While the ECR activity increased after a small amount of N doping,it decreased for higher N doping content.Among them,the N:ZnO-1 h electrocatalysts showed the best CO selectivity,with a faradaic efficiency(FE_(CO))of 92.7%at-0.73 V vs.reversible hydrogen electrode(RHE),which was greater than that of an undoped Zn O electrocatalyst(FE_(CO)of 63.4%at-0.78 V_(RHE)).Also,the N:ZnO-1 h electrocatalyst exhibited outstanding durability for 16 h,with a partial current density of-92.1 mA cm^(-2).This improvement of N:ZnO-1 h electrocatalyst can be explained by density functional theory calculations,demonstrating that this improvement of N:ZnO-1 h electrocatalyst comes from(ⅰ)the optimized active sites lowering the free energy barrier for the rate-determining step(RDS),and(ⅱ)the modification of electronic structure enhancing the electron transfer rate by N doping.

Surface-modified Ag@Ru-P25 for photocatalytic CO_(2) conversion with high selectivity over CH_(4) formation at the solid–gas interface

Systematic optimization of the photocatalyst and investigation of the role of each component is important to maximizing catalytic activity and comprehending the photocatalytic conversion of CO_(2) reduction to solar fuels.A surface-modified Ag@Ru-P25 photocatalyst with H_(2)O_(2) treatment was designed in this study to convert CO_(2) and H_(2)O vapor into highly selective CH4.Ru doping followed by Ag nanoparticles(NPs)cocatalyst deposition on P25(TiO_(2))enhances visible light absorption and charge separation,whereas H_(2)O_(2) treatment modifies the surface of the photocatalyst with hydroxyl(–OH)groups and promotes CO_(2) adsorption.High-resonance transmission electron microscopy,X-ray photoelectron spectroscopy,X-ray absorption near-edge structure,and extended X-ray absorption fine structure techniques were used to analyze the surface and chemical composition of the photocatalyst,while thermogravimetric analysis,CO_(2) adsorption isotherm,and temperature programmed desorption study were performed to examine the significance of H_(2)O_(2) treatment in increasing CO_(2) reduction activity.The optimized Ag1.0@Ru1.0-P25 photocatalyst performed excellent CO_(2) reduction activity into CO,CH4,and C2H6 with a~95%selectivity of CH4,where the activity was~135 times higher than that of pristine TiO_(2)(P25).For the first time,this work explored the effect of H_(2)O_(2) treatment on the photocatalyst that dramatically increases CO_(2) reduction activity.

镍纳米颗粒调控MOF基镍-氮碳催化剂高效电催化还原CO_(2)的研究

通过碳化负载镍络合物的沸石咪唑骨架(ZIF-8)合成了一种高性能镍-氮-碳催化剂(Ni-NC)。通过透射电镜､BET､X射线光电子能谱仪对材料的多孔结构及金属-氮的配位情况进行表征。结果表明,合成的Ni-NC催化剂表现出优异的CO_(2)ER活性和选择性:在较低的过电位490 mV下达到92.6%的CO法拉第效率,并在-0.7 V达到最大值94.6%,电流密度为20.6 mA/cm^(2),性能优于未负载镍的氮掺杂多孔碳,表明镍纳米颗粒在催化反应过程中起着至关重要的作用。此外,在10 h的电解中,CO法拉第效率可保持在90%以上。合成的Ni-NC催化剂在电催化还原CO_(2)为CO方面具有广阔的应用前景。

Analysis of pressure response at an observation well against pressure build-up by early stage of CO_(2)geological storage project

To ensure a safe and stable CO_(2)storage,pressure responses at an observation well are expected to be an important and useful field monitoring item to estimate the CO_(2)storage behaviors and the aquifer parameters during and after injecting CO_(2),because it can detect whether the injected CO_(2)leaks to the ground surface or the bottom of the sea.In this study,pressure responses were simulated to present design factors such as well location and pressure transmitter of the observation well.Numerical simulations on the pressure response and the time-delay from pressure build-up after CO_(2)injection were conducted by considering aquifer parameters and distance from the CO_(2)injection well to an observation well.The measurement resolution of a pressure transmitter installed in the observation well was presented based on numerical simulation results of the pressure response against pressure build-up at the injection well and CO_(2)plume front propagations.Furthermore,the pressure response at an observation well was estimated by comparing the numerical simulation results with the curve of CO_(2)saturation and relative permeability.It was also suggested that the analytical solution can be used for the analysis of the pressure response tendency using pressure build-up and dimensionless parameters of hydraulic diffusivity.Thus,a criterion was established for selecting a pressure transducer installed at an observation well to monitor the pressure responses with sufficient accuracy and resolution,considering the distance from the injection well and the pressure build-up at the injection well,for future carbon capture and storage(CCS)projects.

A review of interaction mechanisms and microscopic simulation methods for CO_(2)-water-rock system

This work systematically reviews the complex mechanisms of CO_(2)-water-rock interactions,microscopic simulations of reactive transport(dissolution,precipitation and precipitate migration)in porous media,and microscopic simulations of CO_(2)-water-rock system.The work points out the key issues in current research and provides suggestions for future research.After injection of CO_(2) into underground reservoirs,not only conventional pressure-driven flow and mass transfer processes occur,but also special physicochemical phenomena like dissolution,precipitation,and precipitate migration.The coupling of these processes causes complex changes in permeability and porosity parameters of the porous media.Pore-scale microscopic flow simulations can provide detailed information within the three-dimensional pore and throat space and explicitly observe changes in the fluid-solid interfaces of porous media during reactions.At present,the research has limitations in the decoupling of complex mechanisms,characterization of differential multi-mineral reactions,precipitation generation mechanisms and characterization(crystal nucleation and mineral detachment),simulation methods for precipitation-fluid interaction,and coupling mechanisms of multiple physicochemical processes.In future studies,it is essential to innovate experimental methods to decouple“dissolution-precipitation-precipitate migration”processes,improve the accuracy of experimental testing of minerals geochemical reaction-related parameters,build reliable characterization of various precipitation types,establish precipitation-fluid interaction simulation methods,coordinate the boundary conditions of different physicochemical processes,and,finally,achieve coupled flow simulation of“dissolution-precipitation-precipitate migration”within CO_(2)-water-rock systems.

Demonstration of a small‐scale power generator using supercritical CO_(2)

The supercritical CO_(2)(sCO_(2))power cycle could improve efficiencies for a wide range of thermal power plants.The sCO_(2)turbine generator plays an important role in the sCO_(2)power cycle by directly converting thermal energy into mechanical work and electric power.The operation of the generator encounters challenges,including high temperature,high pressure,high rotational speed,and other engineering problems,such as leakage.Experimental studies of sCO_(2)turbines are insufficient because of the significant difficulties in turbine manufacturing and system construction.Unlike most experimental investigations that primarily focus on 100 kW‐or MW‐scale power generation systems,we consider,for the first time,a small‐scale power generator using sCO_(2).A partial admission axial turbine was designed and manufactured with a rated rotational speed of 40,000 rpm,and a CO_(2)transcritical power cycle test loop was constructed to validate the performance of our manufactured generator.A resistant gas was proposed in the constructed turbine expander to solve the leakage issue.Both dynamic and steady performances were investigated.The results indicated that a peak electric power of 11.55 kW was achieved at 29,369 rpm.The maximum total efficiency of the turbo‐generator was 58.98%,which was affected by both the turbine rotational speed and pressure ratio,according to the proposed performance map.

CO_(2) hydrogenation to methanol over the copper promoted In_(2)O_(3) catalyst

The metal promoted In_(2)O_(3) catalysts for CO_(2) hydrogenation to methanol have attracted wide attention because of their high activity with high methanol selectivity.However,there was still no experimental confirmation if copper could be a good promoter for In_(2)O_(3).Herein,the Cu promoted In_(2)O_(3) catalyst was prepared using a deposition-precipitation method.Such prepared Cu/In_(2)O_(3) catalyst shows significantly higher CO_(2) conversion and space time yield(STY)of methanol,compared to the un-promoted In_(2)O_(3) catalyst.The loading of Cu facilitates the activation of both H_(2) and CO_(2) with the interface between the Cu cluster and defective In_(2)O_(3) as the active site.The Cu/In_(2)O_(3) catalyst takes the CO hydrogenation pathway for methanol synthesis from CO_(2) hydrogenation.It exhibits a unique size effect on the CO adsorption.At temperatures below 250℃,CO adsorption on Cu/In_(2)O_(3) is stronger than that on In_(2)O_(3),causing higher methanol selectivity.With increasing temperatu res,the Cu catalyst aggregates,which leads to the formation of weak CO adsorption site and causes a decrease in the methanol selectivity.Compared with other metal promoted In_(2)O_(3) catalysts,it can be concluded that the catalyst with stronger CO adsorption possesses higher methanol selectivity.

Reconcile the contradictory wettability requirements for the reduction and oxidation half-reactions in overall CO_(2) photoreduction via alternately hydrophobic surfaces

The overall photocatalytic CO_(2) reduction reaction(OPCRR)that can directly convert CO_(2) and H_(2)O into fuels represents a promising renewable energy conversion technology.As a typical redox reaction,the OPCRR involves two half-reactions:the CO_(2) reduction half-reaction(CRHR)and the water oxidation half-reaction(WOHR).Generally,both half-reactions can be promoted by adjusting the wettability of catalysts.However,there is a contradiction in wettability requirements for the two half-reactions.Specifically,CRHR prefers a hydrophobic surface that can accumulate more CO_(2) molecules on the active sites,ensuring the appropriate ratio of gas-phase(CO_(2))to liquid-phase(H_(2)O)reactants.Conversely,the WOHR prefers a hydrophilic surface that can promote the departure of the gaseous product(O_(2))from the catalyst surface,preventing isolation between active sites and the reactant(H_(2)O).Here,we successfully reconciled the contradictory wettability requirements for the CRHR and WOHR by creating an alternately hydrophobic catalyst.This was achieved through a selectively hydrophobic modification method and a charge-transfer-control strategy.Consequently,the collaboratively promoted CRHR and WOHR led to a significantly enhanced OPCRR with a solar-to-fuel conversion efficiency of 0.186%.Notably,in ethanol production,the catalyst exhibited a 10.64-fold increase in generation rate(271.44μmol g^(-1)h~(-1))and a 4-fold increase in selectivity(55.77%)compared to the benchmark catalyst.This innovative approach holds great potential for application in universal overall reactions involving gas participation.

Electron-deficient ZnO induced by heterointerface engineering as the dominant active component to boost CO_(2)-to-formate conversion

Electrocatalytic CO_(2)-to-formate conversion is considered an economically viable process.In general,Zn-based nanomaterials are well-known to be highly efficient electrocatalysts for the conversion of CO_(2) to CO,but seldom do they exhibit excellent selectivity toward formate.In this article,we demonstrate that a heterointerface catalyst ZnO/ZnSnO3 with nanosheet morphology shows enhanced selectivity with a maximum Faradaic efficiency(FE)of 86%at−0.9 V versus reversible hydrogen electrode and larger current density for the conversion of CO_(2) to formate than pristine ZnO and ZnSnO3.In particular,the FEs of the C1 products(CO+HCOO−)exceed 98%over the potential window.The experimental measurements combined with theoretical calculations revealed that the ZnO in ZnO/ZnSnO3 heterojunction delivers the valence electron depletion and accordingly optimizes Zn d-band center,which results in moderate Zn-O hybridization of HCOO*and weakened Zn-C hybridization of competing COOH*,thus greatly boosting the HCOOH generation.Our study highlights the importance of charge redistribution in catalysts on the selectivity of electrochemical CO_(2) reduction.