Hydrate-based CO_(2) sequestration is an effective method for reducing the greenhouse effect,and the presence of porous media and NaCl can impact the formation characteristics of hydrates.This study uses the constant ...Hydrate-based CO_(2) sequestration is an effective method for reducing the greenhouse effect,and the presence of porous media and NaCl can impact the formation characteristics of hydrates.This study uses the constant volume temperature search method to investigate the effects of quartz sand particle size(0.006‒0.03 mm),water saturation(30%–90%),and NaCl concentration(1%‒9%)on the phase equilibrium and kinetics of CO_(2) hydrates within a temperature range of 273‒285 K and pressure range of 1.0‒3.5 MPa.The results indicate that a decrease in quartz sand particle size or an increase in NaCl concentration shifts the hydrate phase equilibrium curve towards lower temperatures and higher pressures,making hydrate generation conditions more demanding.In different particle size systems,there are no significant changes in the rate of CO_(2) hydrate formation or conversion rate.The highest hydrate conversion rate of 71.1%is observed in a 0.015 mm particle size system.With increasing water saturation,both the generation rate and conversion rate of CO_(2) hydrates show a trend of first increasing and then decreasing.Meanwhile,low concentrations of NaCl(1%–3%)are found to enhance the formation and conversion rates of CO_(2) hydrates.However,as NaCl concentration increases,the rate of CO_(2) hydrate formation and conversion rate decrease.展开更多
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 spect...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.展开更多
The mechanisms of weld formation, spatter and projected transfer in CO2 arc welding are revealed based on the experiment and study of the arc physics. The views are beneficial to develop CO2 arc welding technology.
Electrical double-layer capacitors(EDLCs)consist of energy storage devices that present high-power and moderate energy density.The electrolyte and electrode physicochemical properties are crucial for improving their o...Electrical double-layer capacitors(EDLCs)consist of energy storage devices that present high-power and moderate energy density.The electrolyte and electrode physicochemical properties are crucial for improving their overall energy storage capabilities.Therefore,the stability of the EDLCs’materials is the primary focus of this study.Since energy storage depends on the specific capacitance,and also on the square of the maximum capacitive cell voltage(UMCV).Thus,electrodes with high specific surface area(SSA)and electrolytes with excellent electrochemical stability are commonly reported in the literature.Aqueous electrolytes are safer and green devices compared to other organic-based solutions.On the other hand,their UMCVis reduced compared to other electrolytes(e.g.,organic-based and ionic liquids).In this sense,spanning the UMCVfor aqueous-based electrolytes is a’hot topic’research.Unfortunately,the lack of protocols to establish reliable UMCVvalues has culminated in the publishing of several conflicting results.Herein,we confirm that multiwalled carbon nanotubes(MWCNTs)housed in cells degrade and produce CO_(2) under abusive polarisation conditions.It is probed by employing electrochemical techniques,in-situ FTIR and in-situ Raman spectroscopies.From these considerations,the current study uses spectro-electrochemical techniques to support the correct determination of the electrode and electrolyte stability conditions as a function of the operating electrochemical parameters.展开更多
The electrochemical carbon dioxide reduction(eCO_(2)RR)to formate,driven by clean energy,is a promising approach for producing renewable chemicals and high-value fuels.Despite its potential,further development faces c...The electrochemical carbon dioxide reduction(eCO_(2)RR)to formate,driven by clean energy,is a promising approach for producing renewable chemicals and high-value fuels.Despite its potential,further development faces challenges due to limitations in electrocatalytic activity and durability,especially for nonnoble metal-based catalysts.Here,naturally abundant bismuth-based nanosheets that can effectively drive CO_(2)-to-formate electrocatalytic reduction are prepared using the plasma-activated Bi_(2)Se_(3) followed by a reduction process.Thus-obtained plasma-activated Bi nanosheets(P-BiNS)feature ultrathin structures and high surface areas.Such nanostructures ensure the P-BiNS with outstanding eCO_(2)RR catalytic performance,highlighted by the current density of over 80 mA cm^(-2) and a formate Faradic efficiency of>90%.Furthermore,P-BiNS catalysts demonstrate excellent durability and stability without deactivation following over 50h of operation.The selectivity for formate production is also studied by density functional theory(DFT)calculations,validating the importance and efficacy of the stabilization of intermediates(^(*)OCHO)on the P-BiNS surfaces.This study provides a facile plasma-assisted approach for developing high-performance and low-cost electrocatalysts.展开更多
São Paulo State has witnessed CO_(2)storage-based investigations considering the availability of suitable geologic structures and proximity to primary CO_(2)source sinks related to bioenergy and carbon capture an...São Paulo State has witnessed CO_(2)storage-based investigations considering the availability of suitable geologic structures and proximity to primary CO_(2)source sinks related to bioenergy and carbon capture and storage(BECCS)activities.The current study presents the hydrocarbon viability evaluations and CO_(2)storage prospects,focusing on the sandstone units of the Rio Bonito Formation.The objective is to apply petrophysical evaluations with geochemical inputs in predicting future hydrocarbon(gas)production to boost CO_(2)storage within the study location.The study used data from eleven wells with associated wireline logs(gamma ray,resistivity,density,neutron,and sonic)to predict potential hydrocarbon accumulation and fluid mobility in the investigated area.Rock samples(shale and carbonate)obtained from depths>200 m within the study location have shown bitumen presence.Organic geochemistry data of the Rio Bonito Formation shale beds suggest they are potential hydrocarbon source rocks and could have contributed to the gas accumulations within the sandstone units.Some drilled well data,e.g.,CB-1-SP and TI-1-SP,show hydrocarbon(gas)presence based on the typical resistivity and the combined neutron-density responses at depths up to 3400 m,indicating the possibility of other hydrocarbon members apart from the heavy oil(bitumen)observed from the near-surface rocks samples.From the three-dimensional(3-D)model,the free fluid indicator(FFI)is more significant towards the southwest and southeast of the area with deeper depths of occurrence,indicating portions with reasonable hydrocarbon recovery rates and good prospects for CO_(2)injection,circulation and permanent storage.However,future studies based on contemporary datasets are required to establish the hydrocarbon viability further,foster gas production events,and enhance CO_(2)storage possibilities within the region.展开更多
For electrochemical CO_(2) reduction to HCOOH,an ongoing challenge is to design energy efficient electrocatalysts that can deliver a high HCOOH current density(JHCOOH)at a low overpotential.Indium oxide is good HCOOH ...For electrochemical CO_(2) reduction to HCOOH,an ongoing challenge is to design energy efficient electrocatalysts that can deliver a high HCOOH current density(JHCOOH)at a low overpotential.Indium oxide is good HCOOH production catalyst but with low con-ductivity.In this work,we report a unique corn design of In_(2)O_(3-x)@C nanocatalyst,wherein In_(2)O_(3-x)nanocube as the fine grains dispersed uniformly on the carbon nanorod cob,resulting in the enhanced conductivity.Excellent performance is achieved with 84%Faradaic efficiency(FE)and 11 mA cm^(−2)JHCOOH at a low potential of−0.4 V versus RHE.At the current density of 100 mA cm^(−2),the applied potential remained stable for more than 120 h with the FE above 90%.Density functional theory calculations reveal that the abundant oxygen vacancy in In_(2)O_(3-x) has exposed more In^(3+) sites with activated electroactivity,which facilitates the formation of HCOO*intermediate.Operando X-ray absorp-tion spectroscopy also confirms In^(3+) as the active site and the key intermediate of HCOO*during the process of CO_(2) reduction to HCOOH.展开更多
Electrochemical CO_(2)reduction to formate is a potential approach to achieving global carbon neutrality.Here,Cu1Bi1bimetallic catalyst was prepared by a co-precipitation method.It has a ginger like composite structur...Electrochemical CO_(2)reduction to formate is a potential approach to achieving global carbon neutrality.Here,Cu1Bi1bimetallic catalyst was prepared by a co-precipitation method.It has a ginger like composite structure(CuO/CuBi_(2)O_(4))and exhibited a high formate faradaic efficiency of 98.07%at–0.98 V and a large current density of–56.12 mA.cm^(-2)at–1.28 V,which is twice as high as Bi2O3catalyst.Especially,high selectivity(FE^(–)_(HCOO)>85%)is maintained over a wide potential window of 500 mV.In-situ Raman measurements and structure characterization revealed that the reduced Cu1Bi1bimetallic catalyst possesses abundant Cu-Bi interfaces and residual Bi-O structures.The abundant Cu-Bi interface structures on the catalyst surface can provide abundant active sites for CO_(2)RR,while the Bi-O structures may stabilize the CO_(2)^(*–)intermediate.The synergistic effect of abundant Cu-Bi interfaces and Bi-O species promotes the efficient synthesis of formate by following the OCHO^(*)pathway.展开更多
In this work, a novel thermal–hydraulic–mechanical (THM) coupling model is developed, where the real geological parameters of the reservoir properties are embedded. Accordingly, nine schemes of CO_(2) injection well...In this work, a novel thermal–hydraulic–mechanical (THM) coupling model is developed, where the real geological parameters of the reservoir properties are embedded. Accordingly, nine schemes of CO_(2) injection well (IW) and CH_(4) production well (PW) are established, aiming to explore the behavior of free gases after CO_(2) is injected into the depleted Wufeng–Longmaxi shale. The results indicate the free CH4 or CO2 content in the shale fractures/matrix is invariably heterogeneous. The CO_(2) involvement facilitates the ratio of free CH_(4)/CO_(2) in the matrix to that in the fractures declines and tends to be stable with time. Different combinations of IW–PWs induce a difference in the ratio of the free CH4 to the free CO_(2), in the ratio of the free CH_(4)/CO_(2) in the matrix to that in the fractures, in the content of the recovered free CH_(4), and in the content of the trapped free CO_(2). Basically, when the IW locates at the bottom Wufeng–Longmaxi shale, a farther IW–PWs distance allows more CO2 in the free phase to be trapped;furthermore, no matter where the IW is, a shorter IW–PWs distance benefits by getting more CH_(4) in the free phase recovered from the depleted Wufeng–Longmaxi shale. Hopefully, this work is helpful in gaining knowledge about the shale-based CO_(2) injection technique.展开更多
The conversion of CO_(2) into fuels and valuable chemicals is one of the central topics to combat climate change and meet the growing demand for renewable energy.Herein,we show that the formate dehydrogenase from Clos...The conversion of CO_(2) into fuels and valuable chemicals is one of the central topics to combat climate change and meet the growing demand for renewable energy.Herein,we show that the formate dehydrogenase from Clostridium ljungdahlii(ClFDH)adsorbed on electrodes displays clear characteristic voltammetric signals that can be assigned to the reduction and oxidation potential of the[4Fe-4S]^(2+/+)cluster under nonturnover conditions.Upon adding substrates,the signals transform into a specific redox center that engages in catalytic electron transport.ClFDH catalyzes rapid and efficient reversible interconversion between CO_(2) and formate in the presence of substrates.The turnover frequency of electrochemical CO_(2) reduction is determined as 1210 s^(-1) at 25℃ and pH 7.0,which can be further enhanced up to 1786 s^(-1) at 50℃.The Faradaic efficiency at−0.6 V(vs.standard hydrogen electrode)is recorded as 99.3%in a 2-h reaction.Inhibition experiments and theoretical modeling disclose interesting pathways for CO_(2) entry,formate exit,and OCN−competition,suggesting an oxidation-state-dependent binding mechanism of catalysis.Our results provide a different perspective for understanding the catalytic mechanism of FDH and original insights into the design of synthetic catalysts.展开更多
Electrochemical reduction of Bi-based metal oxides is regarded as an effective strategy to rationally design advanced electrocatalysts for electrochemical CO_(2)reduction reaction(CO_(2)RR).Realizing high selectivity ...Electrochemical reduction of Bi-based metal oxides is regarded as an effective strategy to rationally design advanced electrocatalysts for electrochemical CO_(2)reduction reaction(CO_(2)RR).Realizing high selectivity at high current density is important for formate production,but remains challenging.Herein,the BiIn hybrid electrocatalyst,deriving from the Bi2O3/In2O3heterojunction(MOD-Biln),shows excellent catalytic performance for CO_(2)RR.The Faradaic efficiency of formate(FEHCOO-) can be realized over 90% at a wide potential window from-0.4 to-1.4 V vs.RHE,while the partial current density of formate(jHCOO-) reaches about 136.7 mA cm^(-2)at-1.4 V in flow cell without IR-compensation.In additio n,the MOD-Biln exhibits superior stability with high selectivity of formate at 100 mA cm^(-2).Systematic characterizations prove the optimized catalytic sites and interface charge transfer of MOD-Biln,while theoretical calculation confirms that the hybrid structure with dual Bi/In metal sites contribute to the optimal free energy of*H and*OCHO intermediates on MOD-Biln surface,thus accelerating the formation and desorption step of*HCOOH to final formate production.Our work provides a facile and useful strategy to develop highly-active and stable electrocatalysts for CO_(2)RR.展开更多
CO_(2)sequestration in marine sediments as solid hydrates is a potential way to capture and store anthropogenic CO_(2).In this study,hydrate formation from liquid CO_(2)in marine sediments was simulated in a glass bea...CO_(2)sequestration in marine sediments as solid hydrates is a potential way to capture and store anthropogenic CO_(2).In this study,hydrate formation from liquid CO_(2)in marine sediments was simulated in a glass beads bed,and the factors affecting the kinetics of hydrate formation were investigated.The results indicated that the rapid initial hydrate formation with a high driving force always increases the mass transfer resistance,which slows down hydrate growth.The final ratio of water conversion is higher under conditions of low temperature and higher pressure.A smaller particle size is conductive to initial CO_(2)hydrate growth,but the water conversion ratio in a bed with larger particles is slightly higher.Compared with other factors,the change in water saturation has an obvious effect on the final water conversion.To inhibit the initial hydrate formation during the injection process,in this paper,a kinetic inhibitor is proposed for pre-injection into marine sediments.This work shows that at a low pressure,a lowconcentration inhibitor has an obvious inhibition effect on hydrate growth.However,at a high pressure,it is necessary to increase the concentration of inhibitor to produce an obvious inhibition effect.展开更多
The conversion of carbon dioxide(CO_(2))into high-value added energy fuels and chemicals(CO,formate,C_(2)H_(4),etc.)through electrochemical reduction(eCO_(2)R)is a promising avenue to sustainable development.However,l...The conversion of carbon dioxide(CO_(2))into high-value added energy fuels and chemicals(CO,formate,C_(2)H_(4),etc.)through electrochemical reduction(eCO_(2)R)is a promising avenue to sustainable development.However,low selectivity,barren activity and poor stability of the electrodes hinder the large-scale application of eCO_(2)R.Herein,we reported a copper-indium-organic-framework(CuIn-MOF)based high-performance catalyst for eCO_(2)R.Elec-trochemical measurement results reveal that CuIn-MOF exhibits high Faradaic efficiency(FE)of CO and formate(300 mV,FE_(CO)=78.6%at-0.86 V vs.RHE,FE_(HCOO^(-))=48.4%at-1.16 V vs.RHE,respectively)in a broad range of current density(20.1–88.4 mA cm^(-2))with long-term stability(6 h)for eCO_(2)R in 0.5 M KHCO_(3)electrolyte solution.Specifically,through anion-regulation engineering,SO_(4)^(2-)anion precursor is more beneficial for the formic acid generation than NO_(3)^(-)anion precursor;while for SO_(4)^(2-)anion precursor,Cu plays a positive regulating role in eCO_(2)R to CO compared to In.Additionally,the high performance in a home-made eCO_(2)R reactor derives benefit from enhanced intrinsic activity and charge re-distribution can be attributed to the formation of In-doped Cu layer.展开更多
CO_(2)dissolution into an aqueous phase and water evaporation into a gaseous phase takes place during CO_(2)injection into an oil reservoir.This study aims to evaluate the phase behaviors of the oil-gas-water system i...CO_(2)dissolution into an aqueous phase and water evaporation into a gaseous phase takes place during CO_(2)injection into an oil reservoir.This study aims to evaluate the phase behaviors of the oil-gas-water system in the displacement of crude oil by CO_(2).The composition of the JL oilfield in the northeast of China is taken as an example.The flash calculation of the oil-gas-water system was performed,based on the method presented by Li and Nghiem.The research results show that CO_(2)dissolution in the aqueous phase declines as the NaCl concentration in formation water rises.CO_(2)injection is beneficial for the evaporation of formation water.The NaCl concentration in formation water has little effect on water evaporation and dissolved-gas escape.When the injection-gas mole fraction of CO_(2)is 0.5,CO_(2)injection can reverse the phase behavior of the petroleum mixture and the oil-gas system is converted to a pure gas-condensate system.For CO_(2)injection,water vapor has little effect on the miscibility of multiple contacts,but can reduce the miscibility of the first contact.展开更多
Electrochemical CO_(2)reduction reaction(CO_(2)RR)driven by sustainable energy has emerged as an attractive route to achieve the target of carbon neutral.Formate is one of the most economically viable products,and ele...Electrochemical CO_(2)reduction reaction(CO_(2)RR)driven by sustainable energy has emerged as an attractive route to achieve the target of carbon neutral.Formate is one of the most economically viable products,and electrocatalytic CO_(2)RR to formate is a promising technology.High-pressure H-cell electrolyzer is easy to operate and allows high CO_(2)solubility for realizing high current density,but the design of highly efficient catalysts for working under high CO_(2)pressures remains challenging.Bismuth-based catalysts exhibit high formate selectivity,but suffer from limited activity.Here,we report a high-performance catalyst,which is derived from BiPO_(4)nanopolyhedrons during electrocatalytic CO_(2)RR to formate in neutral solution under high CO_(2)pressures.A high partial current density of formate(534 mA cm^(−2))and formate formation rate(9.9 mmol h^(−1) cm^(−2))with a formate Faradaic efficiency of 90%have been achieved over BiPO_(4)-derived catalyst at an applied potential of−0.81 V vs.RHE under 3.0 MPa CO_(2)pressure.We discover that BiPO_(4)nanopolyhedrons evolve into metallic Bi nanosheets with rich grain boundaries in electrocatalytic CO_(2)RR under high CO_(2)pressures,and the grain boundaries of the BiPO_(4)-derived catalyst play a vital role in promoting electrocatalytic CO_(2)RR to formate.Our theoretical studies reveal that the charge redistribution occurs at the grain boundaries of Bi surface,and this promotes CO_(2)activation and increases HCOO^(*)intermediate stability,thus making the pathway for CO_(2)RR to formate more selective and energy-favorable.This work not only demonstrates a highly efficient catalyst for CO_(2)RR to formate but also discovers a unique feature of catalyst evolution under high CO_(2)pressures.展开更多
Electrochemical CO_(2)reduction into energy-carrying compounds,such as formate,is of great importance for carbon neutrality,which however suffers from high electrical energy input and liquid products crossover.Herein,...Electrochemical CO_(2)reduction into energy-carrying compounds,such as formate,is of great importance for carbon neutrality,which however suffers from high electrical energy input and liquid products crossover.Herein,we fabricated self-supported ultrathin NiCo layered double hydroxides(LDHs)electrodes as anode for methanol electrooxidation to achieve a high formate production rate(5.89 mmol h^(-1)cm^(-2))coupled with CO_(2)electro-reduction at the cathode.A total formate faradic efficiency of both anode for methanol oxidation and cathode for CO_(2)reduction can reach up to 188%driven by a low cell potential of only 2.06 V at 100 mA cm^(-2)in membrane-electrode assembly(MEA).Physical characterizations demonstrated that Ni^(3+)species,formed on the electrochemical oxidation of Ni-containing hydroxide,acted as catalytically active species for the oxidation of methanol to formate.Furthermore,DFT calculations revealed that ultrathin LDHs were beneficial for the formation of Ni^(3+)in hydroxides and introducing oxygen vacancy in NiCo-LDH could decrease the energy barrier of the rate-determining step for methanol oxidation.This work presents a promising approach for fabricating advanced electrodes towards electrocatalytic reactions.展开更多
High-temperature CO_(2)reduction reaction(HT-CO_(2)RR)in solid oxide electrochemical cells(SOECs)features near-unity selectivity,high energy efficiency,and industrial relevant current density for the production of CO,...High-temperature CO_(2)reduction reaction(HT-CO_(2)RR)in solid oxide electrochemical cells(SOECs)features near-unity selectivity,high energy efficiency,and industrial relevant current density for the production of CO,a widely-utilized“building block”in today’s chemical industry.Thus,it offers an intriguing and promising means to radically change the way of chemical manufacturing and achieve carbon neutrality using renewable energy sources,CO_(2),and water.Albeit with the great potential of HT-CO_(2)RR,this carbon utilization approach,unfortunately,has been suffering coke formation that is seriously detrimental to its energy efficiency and operating lifetime.In recent years,much effort has been added to understanding the mechanism of coke formation,managing reaction conditions to mitigate coke formation,and devising coke-formation-free electrode materials.These investigations have substantially advanced the HT-CO_(2)RR toward a practical industrial technology,but the resulting coke formation prevention strategies compromise activity and energy efficiency.Future research may target exploiting the control over both catalyst design and system design to gain selectivity,energy efficiency,and stability synchronously.Therefore,this perspective overviews the progress of research on coke formation in HT-CO_(2)RR,and elaborates on possible future directions that may accelerate its practical implementation at a large scale.展开更多
Formate can be synthesized electrochemically by CO_(2) reduction reaction(CO_(2)RR)or formalde-hyde oxidation reaction(FOR).The CO_(2)RR approach suffers from kinetic-sluggish oxygen evolution reac-tion at the anode.T...Formate can be synthesized electrochemically by CO_(2) reduction reaction(CO_(2)RR)or formalde-hyde oxidation reaction(FOR).The CO_(2)RR approach suffers from kinetic-sluggish oxygen evolution reac-tion at the anode.To this end,an electrochemical sys-tem combining cathodic CO_(2)RR with anodic FOR was developed,which enables the formate electrosynthesis at ultra-low voltage.Cathodic CO_(2)RR employing the BiOCl electrode in H-cell exhibited formate Faradaic efficiency(FE)higher than 90% within a wide potential range from−0.48 to−1.32 V_(RHE).In flow cell,the current density of 100 mA cm^(−2) was achieved at−0.67 V_(RHE).The anodic FOR using the Cu_(2)O electrode displayed a low onset potential of−0.13 V_(RHE) and nearly 100%formate and H_(2) selectivity from 0.05 to 0.35 V_(RHE).The CO_(2)RR and FOR were constructed in a flow cell through membrane electrode assembly for the electrosynthesis of formate,where the CO_(2)RR//FOR delivered an enhanced current density of 100 mA cm^(−2) at 0.86 V.This work provides a promising pair-electrosynthesis of value-added chemicals with high FE and low energy consumption.展开更多
Electrocatalytic CO_(2)reduction reaction(CO_(2)RR),driven by clean electric energy such as solar and wind,can not only alleviate environmental greenhouse effect stemming from excessive CO_(2)emissions,but also realiz...Electrocatalytic CO_(2)reduction reaction(CO_(2)RR),driven by clean electric energy such as solar and wind,can not only alleviate environmental greenhouse effect stemming from excessive CO_(2)emissions,but also realize the storage of renewable energy,for it guarantees the production of value-added chemicals and fuels.Among CO_(2)RR products,formic acid shows great advantages in low energy consumption and high added-value,and thus producing formic acid is generally considered as a profitable line for CO_(2)RR.Bismuth-based electrocatalysts exhibit high formic acid selectivity in CO_(2)RR.Herein,we review the recent progress in bismuth-based electrocatalysts for CO_(2)RR,including material synthesis,performance optimization/validation,and electrolyzers.The effects of morphologies,structure,and composition of bismuth-based electrocatalysts on CO_(2)RR performance are highlighted.Simultaneously,in situ spectroscopic characterization and DFT calculations for reaction mechanism of CO_(2)RR on Bi-based catalysts are emphasized.The applications and optimization of electrolyzers with high current density for CO_(2)RR are summarized.Finally,conclusions and future directions in this field are prospected.展开更多
Taking copper doped ZnS(ZnS:Cu)nanocrystals as the main body of photocatalyst,the influence of different base transition metal ions(M^(2+)=Ni^(2+),Co^(2+),Fe^(2+)and Cd^(2+))on photocatalytic CO_(2)reduction in inorga...Taking copper doped ZnS(ZnS:Cu)nanocrystals as the main body of photocatalyst,the influence of different base transition metal ions(M^(2+)=Ni^(2+),Co^(2+),Fe^(2+)and Cd^(2+))on photocatalytic CO_(2)reduction in inorganic reaction system is investigated.Confined single-atom Ni^(2+),Co^(2+),and Cd^(2+)sites were created via cation-exchange process and enhanced CO_(2)reduction,while Fe^(2+)suppressed the photocatalytic activity for both water and CO_(2)reduction.The modified ZnS:Cu photocatalysts(M/ZnS:Cu)demonstrated tunable product selectivity,with Ni^(2+)and Co^(2+)showing high selectivity for syngas production and Cd^(2+)displaying remarkable formate selectivity.DFT calculations indicated favorable H adsorption free energy on Ni^(2+)and Co^(2+)sites,promoting the hydrogen evolution reaction.The selectivity of CO_(2)reduction products was found to be sensitive to the initial intermediate adsorption states.*COOH formed on Ni^(2+)and Co^(2+)while*OCHO formed on Cd^(2+),favoring the production of CO and HCOOH as the main products,respectively.This work provides valuable insights for developing efficient solar-to-fuel platforms with controlled CO_(2)reduction selectivity.展开更多
基金the National Natural Science Foundation of China(NSFC 21676145)Priority Academic Program Development of Jiangsu Higher Education Institutions(PAPD,China).
文摘Hydrate-based CO_(2) sequestration is an effective method for reducing the greenhouse effect,and the presence of porous media and NaCl can impact the formation characteristics of hydrates.This study uses the constant volume temperature search method to investigate the effects of quartz sand particle size(0.006‒0.03 mm),water saturation(30%–90%),and NaCl concentration(1%‒9%)on the phase equilibrium and kinetics of CO_(2) hydrates within a temperature range of 273‒285 K and pressure range of 1.0‒3.5 MPa.The results indicate that a decrease in quartz sand particle size or an increase in NaCl concentration shifts the hydrate phase equilibrium curve towards lower temperatures and higher pressures,making hydrate generation conditions more demanding.In different particle size systems,there are no significant changes in the rate of CO_(2) hydrate formation or conversion rate.The highest hydrate conversion rate of 71.1%is observed in a 0.015 mm particle size system.With increasing water saturation,both the generation rate and conversion rate of CO_(2) hydrates show a trend of first increasing and then decreasing.Meanwhile,low concentrations of NaCl(1%–3%)are found to enhance the formation and conversion rates of CO_(2) hydrates.However,as NaCl concentration increases,the rate of CO_(2) hydrate formation and conversion rate decrease.
基金supported by Russian Science Foundation (No.#21-73-10235)
文摘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.
文摘The mechanisms of weld formation, spatter and projected transfer in CO2 arc welding are revealed based on the experiment and study of the arc physics. The views are beneficial to develop CO2 arc welding technology.
基金the financial support from the Brazilian funding agencies CNPq(301486/2016-6)FAEPEX(2426/17)+7 种基金FAPESP(2020/04431-0,2020/04281-8,2016/25082-8,2017/11986-5,2017/11958-1,2014/02163-7,2018/20756-6,2018/02713-8)CAPES(1740195)the financial support from CNPq(Processes 131234/2020-0 and 130741/2021-3)the Fundação ao AmparoàPesquisa do Estado de Minas Gerais(FAPEMIGCNPq for the PQ-2 grant(Process 310544/20190)the support of Shell,the strategic importance of the support given by Brazil’s National Oil,Natural Gas,and Biofuels Agency(ANP)through the R&D levy regulationthe Center for Innovation on New Energies(CINE)the LNLS/CNPEM。
文摘Electrical double-layer capacitors(EDLCs)consist of energy storage devices that present high-power and moderate energy density.The electrolyte and electrode physicochemical properties are crucial for improving their overall energy storage capabilities.Therefore,the stability of the EDLCs’materials is the primary focus of this study.Since energy storage depends on the specific capacitance,and also on the square of the maximum capacitive cell voltage(UMCV).Thus,electrodes with high specific surface area(SSA)and electrolytes with excellent electrochemical stability are commonly reported in the literature.Aqueous electrolytes are safer and green devices compared to other organic-based solutions.On the other hand,their UMCVis reduced compared to other electrolytes(e.g.,organic-based and ionic liquids).In this sense,spanning the UMCVfor aqueous-based electrolytes is a’hot topic’research.Unfortunately,the lack of protocols to establish reliable UMCVvalues has culminated in the publishing of several conflicting results.Herein,we confirm that multiwalled carbon nanotubes(MWCNTs)housed in cells degrade and produce CO_(2) under abusive polarisation conditions.It is probed by employing electrochemical techniques,in-situ FTIR and in-situ Raman spectroscopies.From these considerations,the current study uses spectro-electrochemical techniques to support the correct determination of the electrode and electrolyte stability conditions as a function of the operating electrochemical parameters.
基金partial support from the Jiujiang Research Institute at Xiamen University.
文摘The electrochemical carbon dioxide reduction(eCO_(2)RR)to formate,driven by clean energy,is a promising approach for producing renewable chemicals and high-value fuels.Despite its potential,further development faces challenges due to limitations in electrocatalytic activity and durability,especially for nonnoble metal-based catalysts.Here,naturally abundant bismuth-based nanosheets that can effectively drive CO_(2)-to-formate electrocatalytic reduction are prepared using the plasma-activated Bi_(2)Se_(3) followed by a reduction process.Thus-obtained plasma-activated Bi nanosheets(P-BiNS)feature ultrathin structures and high surface areas.Such nanostructures ensure the P-BiNS with outstanding eCO_(2)RR catalytic performance,highlighted by the current density of over 80 mA cm^(-2) and a formate Faradic efficiency of>90%.Furthermore,P-BiNS catalysts demonstrate excellent durability and stability without deactivation following over 50h of operation.The selectivity for formate production is also studied by density functional theory(DFT)calculations,validating the importance and efficacy of the stabilization of intermediates(^(*)OCHO)on the P-BiNS surfaces.This study provides a facile plasma-assisted approach for developing high-performance and low-cost electrocatalysts.
基金sponsored by Fundação de Amparoa Pesquisa do Estado de São Paulo(FAPESP)(2014/50279-4,2020/15230-5,2021/06158-1)Shell Brasil.
文摘São Paulo State has witnessed CO_(2)storage-based investigations considering the availability of suitable geologic structures and proximity to primary CO_(2)source sinks related to bioenergy and carbon capture and storage(BECCS)activities.The current study presents the hydrocarbon viability evaluations and CO_(2)storage prospects,focusing on the sandstone units of the Rio Bonito Formation.The objective is to apply petrophysical evaluations with geochemical inputs in predicting future hydrocarbon(gas)production to boost CO_(2)storage within the study location.The study used data from eleven wells with associated wireline logs(gamma ray,resistivity,density,neutron,and sonic)to predict potential hydrocarbon accumulation and fluid mobility in the investigated area.Rock samples(shale and carbonate)obtained from depths>200 m within the study location have shown bitumen presence.Organic geochemistry data of the Rio Bonito Formation shale beds suggest they are potential hydrocarbon source rocks and could have contributed to the gas accumulations within the sandstone units.Some drilled well data,e.g.,CB-1-SP and TI-1-SP,show hydrocarbon(gas)presence based on the typical resistivity and the combined neutron-density responses at depths up to 3400 m,indicating the possibility of other hydrocarbon members apart from the heavy oil(bitumen)observed from the near-surface rocks samples.From the three-dimensional(3-D)model,the free fluid indicator(FFI)is more significant towards the southwest and southeast of the area with deeper depths of occurrence,indicating portions with reasonable hydrocarbon recovery rates and good prospects for CO_(2)injection,circulation and permanent storage.However,future studies based on contemporary datasets are required to establish the hydrocarbon viability further,foster gas production events,and enhance CO_(2)storage possibilities within the region.
基金supported by Natural Science Foundation of China(21972006,U2001217,21771156)Shenzhen Science and Technology Innovation Commission(KCXFZ20201221173604012)+2 种基金Shenzhen Peacock Plan(KQTD2016053015544057)Shenzhen-Hong Kong Innovation Circle United Research Project(SGLH20180622092406130)supported by the U.S.Department of Energy,Office of Science,Office of Basic Energy Sciences,under Contract No.DE-AC02-06CH11357.
文摘For electrochemical CO_(2) reduction to HCOOH,an ongoing challenge is to design energy efficient electrocatalysts that can deliver a high HCOOH current density(JHCOOH)at a low overpotential.Indium oxide is good HCOOH production catalyst but with low con-ductivity.In this work,we report a unique corn design of In_(2)O_(3-x)@C nanocatalyst,wherein In_(2)O_(3-x)nanocube as the fine grains dispersed uniformly on the carbon nanorod cob,resulting in the enhanced conductivity.Excellent performance is achieved with 84%Faradaic efficiency(FE)and 11 mA cm^(−2)JHCOOH at a low potential of−0.4 V versus RHE.At the current density of 100 mA cm^(−2),the applied potential remained stable for more than 120 h with the FE above 90%.Density functional theory calculations reveal that the abundant oxygen vacancy in In_(2)O_(3-x) has exposed more In^(3+) sites with activated electroactivity,which facilitates the formation of HCOO*intermediate.Operando X-ray absorp-tion spectroscopy also confirms In^(3+) as the active site and the key intermediate of HCOO*during the process of CO_(2) reduction to HCOOH.
基金financially supported by the National Natural Science Foundation of China(22172082,21978137,and 21878162)the Natural Science Foundation of Tianjin(20JCZDJC00770)+1 种基金the NCC Fund(NCC2020FH05)the Fundamental Research Funds for the Central Universities。
文摘Electrochemical CO_(2)reduction to formate is a potential approach to achieving global carbon neutrality.Here,Cu1Bi1bimetallic catalyst was prepared by a co-precipitation method.It has a ginger like composite structure(CuO/CuBi_(2)O_(4))and exhibited a high formate faradaic efficiency of 98.07%at–0.98 V and a large current density of–56.12 mA.cm^(-2)at–1.28 V,which is twice as high as Bi2O3catalyst.Especially,high selectivity(FE^(–)_(HCOO)>85%)is maintained over a wide potential window of 500 mV.In-situ Raman measurements and structure characterization revealed that the reduced Cu1Bi1bimetallic catalyst possesses abundant Cu-Bi interfaces and residual Bi-O structures.The abundant Cu-Bi interface structures on the catalyst surface can provide abundant active sites for CO_(2)RR,while the Bi-O structures may stabilize the CO_(2)^(*–)intermediate.The synergistic effect of abundant Cu-Bi interfaces and Bi-O species promotes the efficient synthesis of formate by following the OCHO^(*)pathway.
基金This study was financially supported by the National Natural Science Foundation of China(Grant Nos.51704197 and 11872258)。
文摘In this work, a novel thermal–hydraulic–mechanical (THM) coupling model is developed, where the real geological parameters of the reservoir properties are embedded. Accordingly, nine schemes of CO_(2) injection well (IW) and CH_(4) production well (PW) are established, aiming to explore the behavior of free gases after CO_(2) is injected into the depleted Wufeng–Longmaxi shale. The results indicate the free CH4 or CO2 content in the shale fractures/matrix is invariably heterogeneous. The CO_(2) involvement facilitates the ratio of free CH_(4)/CO_(2) in the matrix to that in the fractures declines and tends to be stable with time. Different combinations of IW–PWs induce a difference in the ratio of the free CH4 to the free CO_(2), in the ratio of the free CH_(4)/CO_(2) in the matrix to that in the fractures, in the content of the recovered free CH_(4), and in the content of the trapped free CO_(2). Basically, when the IW locates at the bottom Wufeng–Longmaxi shale, a farther IW–PWs distance allows more CO2 in the free phase to be trapped;furthermore, no matter where the IW is, a shorter IW–PWs distance benefits by getting more CH_(4) in the free phase recovered from the depleted Wufeng–Longmaxi shale. Hopefully, this work is helpful in gaining knowledge about the shale-based CO_(2) injection technique.
基金support from the National Key Research and Development Program of China (No.2020YFA0907300)the National Natural Science Foundation of China (No.22077069)+1 种基金the Natural Science Foundation of Tianjin (19JCZDJC33400)the Fundamental Research Funds for the Central Universities,Nankai University (63201111).
文摘The conversion of CO_(2) into fuels and valuable chemicals is one of the central topics to combat climate change and meet the growing demand for renewable energy.Herein,we show that the formate dehydrogenase from Clostridium ljungdahlii(ClFDH)adsorbed on electrodes displays clear characteristic voltammetric signals that can be assigned to the reduction and oxidation potential of the[4Fe-4S]^(2+/+)cluster under nonturnover conditions.Upon adding substrates,the signals transform into a specific redox center that engages in catalytic electron transport.ClFDH catalyzes rapid and efficient reversible interconversion between CO_(2) and formate in the presence of substrates.The turnover frequency of electrochemical CO_(2) reduction is determined as 1210 s^(-1) at 25℃ and pH 7.0,which can be further enhanced up to 1786 s^(-1) at 50℃.The Faradaic efficiency at−0.6 V(vs.standard hydrogen electrode)is recorded as 99.3%in a 2-h reaction.Inhibition experiments and theoretical modeling disclose interesting pathways for CO_(2) entry,formate exit,and OCN−competition,suggesting an oxidation-state-dependent binding mechanism of catalysis.Our results provide a different perspective for understanding the catalytic mechanism of FDH and original insights into the design of synthetic catalysts.
基金financially supported by the National Natural Science Foundation of China (Grant Nos. 22205205)the Zhejiang Provincial Natural Science Foundation of China (Grant Nos.LQ22B030008)the Science Foundation of Zhejiang Sci-Tech University (ZSTU)(Grant Nos. 21062337-Y and 22062312-Y)。
文摘Electrochemical reduction of Bi-based metal oxides is regarded as an effective strategy to rationally design advanced electrocatalysts for electrochemical CO_(2)reduction reaction(CO_(2)RR).Realizing high selectivity at high current density is important for formate production,but remains challenging.Herein,the BiIn hybrid electrocatalyst,deriving from the Bi2O3/In2O3heterojunction(MOD-Biln),shows excellent catalytic performance for CO_(2)RR.The Faradaic efficiency of formate(FEHCOO-) can be realized over 90% at a wide potential window from-0.4 to-1.4 V vs.RHE,while the partial current density of formate(jHCOO-) reaches about 136.7 mA cm^(-2)at-1.4 V in flow cell without IR-compensation.In additio n,the MOD-Biln exhibits superior stability with high selectivity of formate at 100 mA cm^(-2).Systematic characterizations prove the optimized catalytic sites and interface charge transfer of MOD-Biln,while theoretical calculation confirms that the hybrid structure with dual Bi/In metal sites contribute to the optimal free energy of*H and*OCHO intermediates on MOD-Biln surface,thus accelerating the formation and desorption step of*HCOOH to final formate production.Our work provides a facile and useful strategy to develop highly-active and stable electrocatalysts for CO_(2)RR.
基金financially supported by the National Natural Science Foundation of China(No.22008258)Tianshan Youth Program in Xinjiang Uygur Autonomous Region(2019Q089)the Scientific Research Program of Universities in Xinjiang Uygur Autonomous Region(XJEDU2019Y069)。
文摘CO_(2)sequestration in marine sediments as solid hydrates is a potential way to capture and store anthropogenic CO_(2).In this study,hydrate formation from liquid CO_(2)in marine sediments was simulated in a glass beads bed,and the factors affecting the kinetics of hydrate formation were investigated.The results indicated that the rapid initial hydrate formation with a high driving force always increases the mass transfer resistance,which slows down hydrate growth.The final ratio of water conversion is higher under conditions of low temperature and higher pressure.A smaller particle size is conductive to initial CO_(2)hydrate growth,but the water conversion ratio in a bed with larger particles is slightly higher.Compared with other factors,the change in water saturation has an obvious effect on the final water conversion.To inhibit the initial hydrate formation during the injection process,in this paper,a kinetic inhibitor is proposed for pre-injection into marine sediments.This work shows that at a low pressure,a lowconcentration inhibitor has an obvious inhibition effect on hydrate growth.However,at a high pressure,it is necessary to increase the concentration of inhibitor to produce an obvious inhibition effect.
基金The authors thank the financial support from the Fundamental Research Funds for the Central Universities(2232022D-18)'Scientific and Technical Innovation Action Plan'Basic Research Field of Shanghai Science and Technology Committee(19JC1410500)Shanghai Sailing Program(22YF1400700).
文摘The conversion of carbon dioxide(CO_(2))into high-value added energy fuels and chemicals(CO,formate,C_(2)H_(4),etc.)through electrochemical reduction(eCO_(2)R)is a promising avenue to sustainable development.However,low selectivity,barren activity and poor stability of the electrodes hinder the large-scale application of eCO_(2)R.Herein,we reported a copper-indium-organic-framework(CuIn-MOF)based high-performance catalyst for eCO_(2)R.Elec-trochemical measurement results reveal that CuIn-MOF exhibits high Faradaic efficiency(FE)of CO and formate(300 mV,FE_(CO)=78.6%at-0.86 V vs.RHE,FE_(HCOO^(-))=48.4%at-1.16 V vs.RHE,respectively)in a broad range of current density(20.1–88.4 mA cm^(-2))with long-term stability(6 h)for eCO_(2)R in 0.5 M KHCO_(3)electrolyte solution.Specifically,through anion-regulation engineering,SO_(4)^(2-)anion precursor is more beneficial for the formic acid generation than NO_(3)^(-)anion precursor;while for SO_(4)^(2-)anion precursor,Cu plays a positive regulating role in eCO_(2)R to CO compared to In.Additionally,the high performance in a home-made eCO_(2)R reactor derives benefit from enhanced intrinsic activity and charge re-distribution can be attributed to the formation of In-doped Cu layer.
基金The National Major Science and Technology Projects of China(2017ZX05030)supported this work。
文摘CO_(2)dissolution into an aqueous phase and water evaporation into a gaseous phase takes place during CO_(2)injection into an oil reservoir.This study aims to evaluate the phase behaviors of the oil-gas-water system in the displacement of crude oil by CO_(2).The composition of the JL oilfield in the northeast of China is taken as an example.The flash calculation of the oil-gas-water system was performed,based on the method presented by Li and Nghiem.The research results show that CO_(2)dissolution in the aqueous phase declines as the NaCl concentration in formation water rises.CO_(2)injection is beneficial for the evaporation of formation water.The NaCl concentration in formation water has little effect on water evaporation and dissolved-gas escape.When the injection-gas mole fraction of CO_(2)is 0.5,CO_(2)injection can reverse the phase behavior of the petroleum mixture and the oil-gas system is converted to a pure gas-condensate system.For CO_(2)injection,water vapor has little effect on the miscibility of multiple contacts,but can reduce the miscibility of the first contact.
文摘Electrochemical CO_(2)reduction reaction(CO_(2)RR)driven by sustainable energy has emerged as an attractive route to achieve the target of carbon neutral.Formate is one of the most economically viable products,and electrocatalytic CO_(2)RR to formate is a promising technology.High-pressure H-cell electrolyzer is easy to operate and allows high CO_(2)solubility for realizing high current density,but the design of highly efficient catalysts for working under high CO_(2)pressures remains challenging.Bismuth-based catalysts exhibit high formate selectivity,but suffer from limited activity.Here,we report a high-performance catalyst,which is derived from BiPO_(4)nanopolyhedrons during electrocatalytic CO_(2)RR to formate in neutral solution under high CO_(2)pressures.A high partial current density of formate(534 mA cm^(−2))and formate formation rate(9.9 mmol h^(−1) cm^(−2))with a formate Faradaic efficiency of 90%have been achieved over BiPO_(4)-derived catalyst at an applied potential of−0.81 V vs.RHE under 3.0 MPa CO_(2)pressure.We discover that BiPO_(4)nanopolyhedrons evolve into metallic Bi nanosheets with rich grain boundaries in electrocatalytic CO_(2)RR under high CO_(2)pressures,and the grain boundaries of the BiPO_(4)-derived catalyst play a vital role in promoting electrocatalytic CO_(2)RR to formate.Our theoretical studies reveal that the charge redistribution occurs at the grain boundaries of Bi surface,and this promotes CO_(2)activation and increases HCOO^(*)intermediate stability,thus making the pathway for CO_(2)RR to formate more selective and energy-favorable.This work not only demonstrates a highly efficient catalyst for CO_(2)RR to formate but also discovers a unique feature of catalyst evolution under high CO_(2)pressures.
基金the financial support from the National Nature Science Foundation of China(22078232 and 21938008)the Haihe Laboratory of Sustainable Chemical Transformations for financial support。
文摘Electrochemical CO_(2)reduction into energy-carrying compounds,such as formate,is of great importance for carbon neutrality,which however suffers from high electrical energy input and liquid products crossover.Herein,we fabricated self-supported ultrathin NiCo layered double hydroxides(LDHs)electrodes as anode for methanol electrooxidation to achieve a high formate production rate(5.89 mmol h^(-1)cm^(-2))coupled with CO_(2)electro-reduction at the cathode.A total formate faradic efficiency of both anode for methanol oxidation and cathode for CO_(2)reduction can reach up to 188%driven by a low cell potential of only 2.06 V at 100 mA cm^(-2)in membrane-electrode assembly(MEA).Physical characterizations demonstrated that Ni^(3+)species,formed on the electrochemical oxidation of Ni-containing hydroxide,acted as catalytically active species for the oxidation of methanol to formate.Furthermore,DFT calculations revealed that ultrathin LDHs were beneficial for the formation of Ni^(3+)in hydroxides and introducing oxygen vacancy in NiCo-LDH could decrease the energy barrier of the rate-determining step for methanol oxidation.This work presents a promising approach for fabricating advanced electrodes towards electrocatalytic reactions.
文摘High-temperature CO_(2)reduction reaction(HT-CO_(2)RR)in solid oxide electrochemical cells(SOECs)features near-unity selectivity,high energy efficiency,and industrial relevant current density for the production of CO,a widely-utilized“building block”in today’s chemical industry.Thus,it offers an intriguing and promising means to radically change the way of chemical manufacturing and achieve carbon neutrality using renewable energy sources,CO_(2),and water.Albeit with the great potential of HT-CO_(2)RR,this carbon utilization approach,unfortunately,has been suffering coke formation that is seriously detrimental to its energy efficiency and operating lifetime.In recent years,much effort has been added to understanding the mechanism of coke formation,managing reaction conditions to mitigate coke formation,and devising coke-formation-free electrode materials.These investigations have substantially advanced the HT-CO_(2)RR toward a practical industrial technology,but the resulting coke formation prevention strategies compromise activity and energy efficiency.Future research may target exploiting the control over both catalyst design and system design to gain selectivity,energy efficiency,and stability synchronously.Therefore,this perspective overviews the progress of research on coke formation in HT-CO_(2)RR,and elaborates on possible future directions that may accelerate its practical implementation at a large scale.
基金This work was supported by the National Key R&D Program of China(2020YFA0710000)the National Natural Science Foundation of China(22122901,21902047)+1 种基金the Provincial Natural Science Foundation of Hunan(2020JJ5045,2021JJ20024,2021RC3054)the Shenzhen Science and Technology Program(JCYJ20210324140610028).
文摘Formate can be synthesized electrochemically by CO_(2) reduction reaction(CO_(2)RR)or formalde-hyde oxidation reaction(FOR).The CO_(2)RR approach suffers from kinetic-sluggish oxygen evolution reac-tion at the anode.To this end,an electrochemical sys-tem combining cathodic CO_(2)RR with anodic FOR was developed,which enables the formate electrosynthesis at ultra-low voltage.Cathodic CO_(2)RR employing the BiOCl electrode in H-cell exhibited formate Faradaic efficiency(FE)higher than 90% within a wide potential range from−0.48 to−1.32 V_(RHE).In flow cell,the current density of 100 mA cm^(−2) was achieved at−0.67 V_(RHE).The anodic FOR using the Cu_(2)O electrode displayed a low onset potential of−0.13 V_(RHE) and nearly 100%formate and H_(2) selectivity from 0.05 to 0.35 V_(RHE).The CO_(2)RR and FOR were constructed in a flow cell through membrane electrode assembly for the electrosynthesis of formate,where the CO_(2)RR//FOR delivered an enhanced current density of 100 mA cm^(−2) at 0.86 V.This work provides a promising pair-electrosynthesis of value-added chemicals with high FE and low energy consumption.
基金This work was financially supported by grants from the National Key Research and Development Program of China(2021YFA1501504)Natural Science Foundation of China(22172135,22288102,92045302,and 22021001).
文摘Electrocatalytic CO_(2)reduction reaction(CO_(2)RR),driven by clean electric energy such as solar and wind,can not only alleviate environmental greenhouse effect stemming from excessive CO_(2)emissions,but also realize the storage of renewable energy,for it guarantees the production of value-added chemicals and fuels.Among CO_(2)RR products,formic acid shows great advantages in low energy consumption and high added-value,and thus producing formic acid is generally considered as a profitable line for CO_(2)RR.Bismuth-based electrocatalysts exhibit high formic acid selectivity in CO_(2)RR.Herein,we review the recent progress in bismuth-based electrocatalysts for CO_(2)RR,including material synthesis,performance optimization/validation,and electrolyzers.The effects of morphologies,structure,and composition of bismuth-based electrocatalysts on CO_(2)RR performance are highlighted.Simultaneously,in situ spectroscopic characterization and DFT calculations for reaction mechanism of CO_(2)RR on Bi-based catalysts are emphasized.The applications and optimization of electrolyzers with high current density for CO_(2)RR are summarized.Finally,conclusions and future directions in this field are prospected.
基金financial support from the Tangshan Talent Funding Project(A202202007)the National Natural Science Foundation of China(21703065)+3 种基金the Natural Science Foundation of Hebei Province(B2018209267)the World Premier International Research Center Initiative(WPI Initiative)on Materials Nanoarchitectonics(MANA),the MEXT(Japan)the Photoexcitonix Project in Hokkaido Universitythe JSPS KAKENHI(Grant Number JP18H02065)。
文摘Taking copper doped ZnS(ZnS:Cu)nanocrystals as the main body of photocatalyst,the influence of different base transition metal ions(M^(2+)=Ni^(2+),Co^(2+),Fe^(2+)and Cd^(2+))on photocatalytic CO_(2)reduction in inorganic reaction system is investigated.Confined single-atom Ni^(2+),Co^(2+),and Cd^(2+)sites were created via cation-exchange process and enhanced CO_(2)reduction,while Fe^(2+)suppressed the photocatalytic activity for both water and CO_(2)reduction.The modified ZnS:Cu photocatalysts(M/ZnS:Cu)demonstrated tunable product selectivity,with Ni^(2+)and Co^(2+)showing high selectivity for syngas production and Cd^(2+)displaying remarkable formate selectivity.DFT calculations indicated favorable H adsorption free energy on Ni^(2+)and Co^(2+)sites,promoting the hydrogen evolution reaction.The selectivity of CO_(2)reduction products was found to be sensitive to the initial intermediate adsorption states.*COOH formed on Ni^(2+)and Co^(2+)while*OCHO formed on Cd^(2+),favoring the production of CO and HCOOH as the main products,respectively.This work provides valuable insights for developing efficient solar-to-fuel platforms with controlled CO_(2)reduction selectivity.