Electrochemical CO_(2) reduction is a sustainable method for producing fuels and chemicals using renewable energy sources.Sn is a widely employed catalyst for formate production,with its performance closely influenced...Electrochemical CO_(2) reduction is a sustainable method for producing fuels and chemicals using renewable energy sources.Sn is a widely employed catalyst for formate production,with its performance closely influenced by the catalyst ink formulations and reac-tion conditions.The present study explores the influence of catalyst loading,current density,and binder choice on Sn-based CO_(2) reduc-tion systems.Decreasing catalyst loading from 10 to 1.685 mg·cm^(-2) and increasing current density in highly concentrated bicarbonate solutions significantly enhances formate selectivity,achieving 88%faradaic efficiency(FE)at a current density of−30 mA·cm^(-2) with a cathodic potential of−1.22 V vs.reversible hydrogen electrode(RHE)and a catalyst loading of 1.685 mg·cm^(-2).This low-loading strategy not only reduces catalyst costs but also enhances surface utilization and suppresses the hydrogen evolution reaction.Nafion enhances formate production when applied as a surface coating rather than pre-mixed in the ink,as evidenced by improved faradaic efficiency and lower cathodic potentials.However,this performance still does not match that of binder-free systems because Sn-based catalysts intrinsic-ally exhibit high catalytic activity,making the binder contribution less significant.Although modifying the electrode surface with binders leads to blocked active sites and increased resistance,polyvinylidene fluoride(PVDF)remains promising because of its stability,strength,and conductivity,achieving up to 72%FE to formate at−30 mA·cm^(-2) and−1.66 V vs.RHE.The findings of this research reveal method-ologies for optimizing the catalyst ink formulations and binder utilization to enhance the conversion of CO_(2) to formate,thereby offering crucial insights for the development of a cost-efficient catalyst for high-current-density operations.展开更多
CO_(2)electrolysis into formate is a promising technology with the potential to simultaneously alleviate energy shortages and global warming.However,the limited stability of the catalysts during long-term electrolysis...CO_(2)electrolysis into formate is a promising technology with the potential to simultaneously alleviate energy shortages and global warming.However,the limited stability of the catalysts during long-term electrolysis hinders their widespread implementation.Herein,we show that a core-shell bimetallic BiAg catalyst with a multifaceted Janus structure at its core can achieve a stability of up to 300 h with a formate faradaic efficiency(FE_(formate))over 90%at−0.75 V vs.RHE(reversible hydrogen electrode)in an H-type cell.Our investigations reveal the important role of the Janus structure on the transfer of electrons,favoring their delocalization across the catalyst and enhancing their mobility.We propose that the compressive strain inclined to grain boundaries within this structure would lower the energy barrier for electrons transfer and promotes the cooperation between Ag and Bi.Indeed,Ag initiates the activation of CO_(2)through a series of cascade reactions and is subsequently hydrogenated on Bi.Additionally,our study suggests that Ag plays a crucial role in stabilizing the catalyst structure after long-term electrolysis.This work highlights a new strategy for tandem CO_(2)electrolysis,providing novel insights for the design of formate formation catalysts.展开更多
CO2 hydrogenation to formate is an effective strategy for promoting the sustainable carbon cycle.However,formate yields are significantly influenced by the amount of noble metal(e.g.,Pd)used.Here,we present Pd-Ni syne...CO2 hydrogenation to formate is an effective strategy for promoting the sustainable carbon cycle.However,formate yields are significantly influenced by the amount of noble metal(e.g.,Pd)used.Here,we present Pd-Ni synergistic catalysis on the hollow NiCo2O4 spinel arrays(PdxNiy/NCO@CC)for enhanced formate production under mild conditions.The Pd-Ni dual-site structure effectively enhances electron accumulation on Pd via charge polarization and the synergistic interaction between Pd and Ni,leading to significantly improved formate yields with a reduced usage of noble metal catalyst.The optimized Pd5Ni5/NCO@CC catalyst achieved a remarkable formate yield of 282.5 molformate molPd^(-1)h^(-1)at 333 K and demonstrated high stability.This strategy of synergistically enhancing catalytic activity via bimetallic sites highlights its advantages in other catalytic fields and practical applications.展开更多
SnS has emerged as an attractive catalyst for the electrochemical CO_(2)reduction reaction(CO_(2)RR)to formate,while its long-term operational stability is hindered by the self-reduction of Sn^(2+) and sulfur dissolut...SnS has emerged as an attractive catalyst for the electrochemical CO_(2)reduction reaction(CO_(2)RR)to formate,while its long-term operational stability is hindered by the self-reduction of Sn^(2+) and sulfur dissolution.Thus,maintaining high current efficiency across a wide negative potential range to achieve high production rates of formate remains a significant challenge.In this study,we present a heterostructure constructed with SnS and CuS for efficient CO_(2)RR to formate.The SnS-CuS(30)exhibits a remarkable formate Faradaic efficiency(FE_(f))of 93.94%at−1 V vs.reversible hydrogen electrode(RHE)and demonstrates long-term stability for 7.5 h,maintaining high activity(with an average FE_(f)of 85.6%)across a wide negative potential range(from-0.8 to-1.2 V(vs.RHE)).The results reveal that the heterogeneous interface between SnS and CuS mitigates the self-reduction issue of SnS by sacrificing Cu^(2+),highlighting that the true active species is SnS,which effectively resists structural changes during the electrolysis process under the protection of CuS.The synergistic interaction within the CuS and SnS heterostructure,combined with the tendency for electron self-conduction,enables the catalyst to maintain high formate activity and selectivity across a wide potential range.Furthermore,theoretical results further indicate that the incorporation of CuS enhances CO_(2)adsorption and lowers the energy barrier for the formation of formate intermediates.This study inspires the concept of applying protective layers to active species,promoting high selectivity in Sn-based electrocatalysts.展开更多
This study investigates using an antioxidation copper particle-free paste,formulated with self-reducing copper formate,for Cu-Cu bonding in electronic packaging applications.The research highlights the oxidation resis...This study investigates using an antioxidation copper particle-free paste,formulated with self-reducing copper formate,for Cu-Cu bonding in electronic packaging applications.The research highlights the oxidation resistance of copper formate compared to traditional copper nanoparticles(CuNPs)and its ability to generate CuNPs through thermal decomposition.Experimental results demonstrate that the sintering process benefits from releasing reductive gases during decomposition,improving joint quality with reduced porosity and enhanced mechanical strength at elevated temperatures.Molecular dynamics simulations further elucidate the sintering behavior of CuNPs,providing significant insights into pore collapse,atomic mobility,and neck formation.The findings indicate that increased temperatures enhance surface and bulk diffusion,facilitating robust particle connections.Overall,this work establishes the potential of copper formate for achieving reliable interconnects in semiconductor devices,paving the way for advancements in material formulations for direct copper–copper bonding.展开更多
Paired electrolysis of waste feedstocks holds an energy-efficient alternative for chemical production;however,the sluggish anodic oxidation limited the total efficiency under larger current density.Herein,we construct...Paired electrolysis of waste feedstocks holds an energy-efficient alternative for chemical production;however,the sluggish anodic oxidation limited the total efficiency under larger current density.Herein,we constructed ultralow-coordinated Ni species with Ni–O coordination number of∼3 via a hydrothermal synthesis-sulfidation-annealing process and electrochemical activation and demonstrated the vital role in accelerating the proton deintercalation and reactive oxygen intermediate·OH formation during electro-reforming polyethylene terephthalate hydrolysate(POR).The target catalyst NiCoSx/NF afforded a high formate productivity of 7.4 mmol cm^(−2)h^(−1)at∼600 mA cm^(−2)with a formate Faradic efficiency(FE_(formate))of 92.4%in POR and maintained a FE_(formate)of∼90%for 100 h at 2 A in a membrane electrode assembly electrolyzer.Coupling POR on NiCoSx/NF with carbon dioxide reduction reaction on oxygen vacancies enriched Vo-BiSnO reached effective concurrent formate production with 172.7%of FE_(formate)at 500 mA cm^(−2)and long-term stability.Such excellent performance shows the great prospect of electrocatalyst design by regulating the local metal environment.展开更多
Leveraging the interplay between the metal component and the supporting material represents a cornerstone strategy for augmenting electrocatalytic efficiency,e.g.,electrocatalytic CO_(2)reduction reaction(CO_(2)RR).He...Leveraging the interplay between the metal component and the supporting material represents a cornerstone strategy for augmenting electrocatalytic efficiency,e.g.,electrocatalytic CO_(2)reduction reaction(CO_(2)RR).Herein,we employ freestanding porous carbon fibers(PCNF)as an efficacious and stable support for the uniformly distributed SnO_(2)nanoparticles(SnO_(2)PCNF),thereby capitalizing on the synergistic support effect that arises from their strong interaction.On one hand,the interaction between the SnO_(2)nanoparticles and the carbon support optimizes the electronic configuration of the active centers.This interaction leads to a noteworthy shift of the d-band center toward stronger intermediate adsorption energy,consequently lowering the energy barrier associated with CO_(2)reduction.As a result,the Sn O_(2)PCNF realizes a remarkable CO_(2)RR performance with excellent selectivity towards formate(98.1%).On the other hand,the porous carbon fibers enable the uniform and stable dispersion of SnO_(2)nanoparticles,and this superior porous structure of carbon supports can also facilitate the exposure of the SnO_(2)nanoparticles on the reaction interface to a great extent.Consequently,adequate contact between active sites,reactants,and electrolytes can significantly increase the metal utilization,eventually bringing forth a remarkable7.09 A/mg mass activity.This work might provide a useful idea for improving the utilization rate of metals in numerous electrocatalytic reactions.展开更多
The selective reduction of carbon dioxide(CO_(2))into high-value-added chemicals is one of the most effective means to solve the current energy and environmental problems,which could realize the utilization of CO_(2) ...The selective reduction of carbon dioxide(CO_(2))into high-value-added chemicals is one of the most effective means to solve the current energy and environmental problems,which could realize the utilization of CO_(2) and promote the balance of the carbon cycle.Formate is one of the most economical and practical products of all the electrochemical CO_(2) reduction products.Among the many metal-based electrocatalysts that can convert CO_(2) into formate,Sn-based catalysts have received a lot of attention because of their low-cost,non-toxic characteristics and high selectivity for formate.In this article,the most recent development of Sn-based electrocatalysts is comprehensively summarized by giving examples,which are mainly divided into monometallic Sn,alloyed Sn,Sn-based compounds and Sn composite catalysts.Finally,the current performance enhancement strategies and future directions of the field are summarized.展开更多
The large current density of electrochemical CO_(2)reduction towards industrial application is challenging.Herein,without strong acid and reductant,the synthesized BiVO_(4)with abundant oxygen vacancies(Ovs)exhibited ...The large current density of electrochemical CO_(2)reduction towards industrial application is challenging.Herein,without strong acid and reductant,the synthesized BiVO_(4)with abundant oxygen vacancies(Ovs)exhibited a high formate Faradaic efficiency(FE)of 97.45%(-0.9 V)and a large partial current density of-45.82 mA/cm^(2)(-1.2 V).The good performance benefits from the reconstruction of BiVO_(4)to generate active metal Bi sites,which results in the electron redistribution to boost the OCHO∗formation.In flow cells,near industrial current density of 183.94 mA/cm^(2)was achieved,with the FE of formate above 95%from 20mA/cm^(2)to 180mA/cm^(2).Our work provides a facily synthesized BiVO_(4)precatalyst for CO_(2)electroreduction.展开更多
The p-block metal(In,Sn,Bi,etc.)-based electrocatalysts have exhibited excellent activity in the electrocatalytic CO_(2)reduction(ECR)to formate.However,the rapid decrease in catalytic activity caused by catalyst reco...The p-block metal(In,Sn,Bi,etc.)-based electrocatalysts have exhibited excellent activity in the electrocatalytic CO_(2)reduction(ECR)to formate.However,the rapid decrease in catalytic activity caused by catalyst reconstruction and agglomeration under ECR conditions significantly restricts their practical applications.Herein,we developed a sulfur anchoring strategy to stabilize the high-density sub-3 nm In_(2)S_(3)nanoparticles on sulfur-doped porous carbon substrates(i-In_(2)S_(3)/S-C)for formate production.Systematic characterizations evidenced that the as-prepared catalyst exhibited a strong metal sulfide-support interaction(MSSI),which effectively regulated the electronic states of In_(2)S_(3),achieving a high formate Faradaic efficiency of 91%at−0.95 V vs.RHE.More importantly,the sulfur anchoring effectively immobilized the sub-3 nm In_(2)S_(3)nanoparticles to prevent them from agglomeration.It enabled the catalysts to exhibit much higher durability than the In_(2)S_(3)samples without sulfur anchoring,demonstrating that the strong MSSI and fast charge transfer on the catalytic interface could significantly promote the structural stability of In_(2)S_(3)catalysts.These results provide a viable approach for developing efficient and stable electrocatalysts for CO_(2)reduction.展开更多
Double bonds of internal olefins can be efficiently migrated to the terminal carbons and regioselectively hydroesterified with formates in the presence of Pd(OAc)_(2) and 1,2-DTBPMB under mild reaction conditions,prov...Double bonds of internal olefins can be efficiently migrated to the terminal carbons and regioselectively hydroesterified with formates in the presence of Pd(OAc)_(2) and 1,2-DTBPMB under mild reaction conditions,providing a wide variety of corresponding linear carboxylic esters bearing various functional groups in good yields and>20:1 linear/branch ratios.The reaction is optionally simple and does not need to use CO gas and acid co-catalysts.展开更多
The electrocatalytic reduction of carbon dioxide(CO_(2)ER)into formate presents a compelling solution for mitigating dependence on fossil energy and green utilization of CO_(2).Bismuth(Bi)has been gaining recognition ...The electrocatalytic reduction of carbon dioxide(CO_(2)ER)into formate presents a compelling solution for mitigating dependence on fossil energy and green utilization of CO_(2).Bismuth(Bi)has been gaining recognition as a promising catalyst material for the CO_(2)ER to formate.The performance of Bi catalysts(named as Bi-V)can be significantly improved when they possess single metal atom vacancy.However,creating larger-sized metal atom vacancies within Bi catalysts remains a significant challenge.In this work,Bi nanosheets with dual V0 Bi vacancy(Bi-DV)were synthesized utilizing in situ electrochemical transformation,using BiOBr nanosheets with triple vacancy associates(V■_(Bi)V··_(O)V■_(Bi),V■_(Bi)and V··_(O)denote the Bi^(3+)and O_(2)−vacancy,respectively)as a template.The obtained Bi-DV achieved higher CO_(2)ER activity than Bi-V,showing Faradaic efficiency for formate production of>92%from-0.9 to-1.2 VRHE in an H-type cell,and the partial current density of formate reached up to 755 mA/cm^(2)in a flow cell.The comprehensive characterizations coupled with density functional theory calculations demonstrate that the dual V^(0)_(Bi)vacancy on the surface of Bi-DV expedite the reaction kinetics toward CO_(2)ER,by reducing the thermodynamic barrier of^(∗)OCHO intermediate formation.This research provides critical insights into the potential of large atom vacancies to enhance electrocatalysis performance.展开更多
CO_(2) electrochemical reduction(CO_(2)ER)is an important research area for carbon neutralization.However,available catalysts for CO_(2) reduction are still characterized by limited stability and activity.Recently,met...CO_(2) electrochemical reduction(CO_(2)ER)is an important research area for carbon neutralization.However,available catalysts for CO_(2) reduction are still characterized by limited stability and activity.Recently,metallic bismuth(Bi)has emerged as a promising catalyst for CO_(2) ER.Herein,we report the solid cathode electroreduction of commercial micronized Bi2O3as a straightforward approach for the preparation of nanostructured Bi.At-1.1 V versus reversible hydrogen electrode in a KHCO3aqueous electrolyte,the resulting nanostructure Bi delivers a formate current density of~40 mA·cm^(-2) with a current efficiency of~86%,and the formate selectivity reaches97.6% at-0.78 V.Using nanosized Bi2O3as the precursor can further reduce the primary particle sizes of the resulting Bi,leading to a significantly increased formate selectivity at relatively low overpotentials.The high catalytic activity of nanostructured Bi is attributable to the ultrafine and interconnected Bi nanoparticles in the nanoporous structure,which exposes abundant active sites for CO_(2) electrocatalytic reduction.展开更多
Electro-reduction of carbon dioxide(ERCO_(2)) is considered an effective method to alleviate the greenhouse effect and produce value-added chemicals.Achieving the dominant selectivity of Zn-based catalysts for formate...Electro-reduction of carbon dioxide(ERCO_(2)) is considered an effective method to alleviate the greenhouse effect and produce value-added chemicals.Achieving the dominant selectivity of Zn-based catalysts for formate remains a challenge.In this article,the ZnIn-E_(12) catalyst is successfully prepared by solvent assisted ligand exchange(SALE) method to convert organic ligands,achieving a Faradaic efficiency of 72.28% for formate at-1.26 V vs.RHE(V_(RHE)),which is 1.42 times higher than the original catalyst.Evidence shows that the successful conversion of organic ligands can transform the catalyst from the original large size polyhedron to cross-linked network of particles with a diameter of about 30 nm.The increased specific surface area can expose more active sites and facilitate the electrocatalytic conversion of CO_(2) to formate.This work is expected to provide inspiration for the regulation of formate selectivity and catalyst size in Zn-based catalysts.展开更多
The corrosion and passive behavior of HP-13Cr stainless steel(HP-13Cr SS)in formate annulus protection fluid was investigated.HP-13Cr SS exhibited good passive behavior in clean formate annulus protection fluid,which ...The corrosion and passive behavior of HP-13Cr stainless steel(HP-13Cr SS)in formate annulus protection fluid was investigated.HP-13Cr SS exhibited good passive behavior in clean formate annulus protection fluid,which was attributed to a thinner and more dense passive film mainly composed of Cr_(2)O_(3).In the formation water solution,the passive film was composed of metastable Cr(OH)3,which was explained by the isoelectric point theory,resulting in the deterioration of the passive behavior of HP-13Cr SS.When the formation water penetrated the formate annulus protection fluid,a large number of loose FeCO_(3)particles formed in the corrosion scales,thus HP-13Cr SS suffered severe corrosion.Therefore,avoiding formation water penetrating the formate annulus protection fluid is conducive to improving the service life of HP-13Cr SS oil tubes in extremely aggressive environment.展开更多
CO_(2)electrochemical reduction reaction(CO_(2)RR)to formate is a hopeful pathway for reducing CO_(2)and producing high-value chemicals,which needs highly selective catalysts with ultra-broad potential windows to meet...CO_(2)electrochemical reduction reaction(CO_(2)RR)to formate is a hopeful pathway for reducing CO_(2)and producing high-value chemicals,which needs highly selective catalysts with ultra-broad potential windows to meet the industrial demands.Herein,the nanorod-like bimetallic ln_(2)O_(3)/Bi_(2)O_(3)catalysts were successfully synthesized by pyrolysis of bimetallic InBi-MOF precursors.The abundant oxygen vacancies generated from the lattice mismatch of Bi_(2)O_(3)and ln_(2)O_(3)reduced the activation energy of CO_(2)to*CO_(2)·^(-)and improved the selectivity of*CO_(2)·^(-)to formate simultaneously.Meanwhile,the carbon skeleton derived from the pyrolysis of organic framework of InBi-MOF provided a conductive network to accelerate the electrons transmission.The catalyst exhibited an ultra-broad applied potential window of 1200 mV(from-0.4 to-1.6 V vs RHE),relativistic high Faradaic efficiency of formate(99.92%)and satisfactory stability after 30 h.The in situ FT-IR experiment and DFT calculation verified that the abundant oxygen vacancies on the surface of catalysts can easily absorb CO_(2)molecules,and oxygen vacancy path is dominant pathway.This work provides a convenient method to construct high-performance bimetallic catalysts for the industrial application of CO_(2)RR.展开更多
CO_(2)-to-formate electrosynthesis with high selectivity and stability has been a long-sought objective.Unfortunately,most catalysts undergo structural and valence state changes due to surface oxidation during operati...CO_(2)-to-formate electrosynthesis with high selectivity and stability has been a long-sought objective.Unfortunately,most catalysts undergo structural and valence state changes due to surface oxidation during operation or storage,resulting in decreased catalytic performance.Herein,we report a efficient and stable BiIn@Cu-foam electrode through the in-situ regeneration of Bi^(0) active sites to renew the surface activation.The electronic structure of Bi site can be regulated by introducing In,thereby enhancing the adsorption strength of*OCHO.The optimized electrode exhibits over 90%FE_(formate)at a wide potential window(-0.9–-2.2 V),and formation rate for 3.15 mM cm^(-1)h^(-1).Especially,the electrode can maintain the high performance at continuously electrolysis for more than 300 h,or for more than 50 cycles,even repeated operation and storage for more than 2 years.This work provides a promising candidate and new insight to construct industrially viable stable Bi-based catalyst for formate electrosynthesis.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
An efficient and sustainable protocol for regioselective hydrocarboxylation of alkynes to construct diverse propionic acid derivatives is disclosed.Under photoinduced conditions,the anti-Markovnikov hydrocarboxylation...An efficient and sustainable protocol for regioselective hydrocarboxylation of alkynes to construct diverse propionic acid derivatives is disclosed.Under photoinduced conditions,the anti-Markovnikov hydrocarboxylation of alkynes was realized with CO_(2) radical anion in-situ generated from formate as both a carbonyl source and a reductant.The collaboration between photosensitizer and hydrogen atom transfer catalyst promoted the catalytic cycle to work smoothly,giving a broad substrate scope including terminal and internal alkynes.The Giese radical addition of CO_(2) radical anion to the C—C triple bond is the key step to initiate the reaction.展开更多
Ever-increasing emissions of anthropogenic carbon dioxide(CO_(2))cause global environmental and climate challenges.Inspired by biological photosynthesis,developing effective strategies NeuNlto up-cycle CO_(2)into high...Ever-increasing emissions of anthropogenic carbon dioxide(CO_(2))cause global environmental and climate challenges.Inspired by biological photosynthesis,developing effective strategies NeuNlto up-cycle CO_(2)into high-value organics is crucial.Electrochemical CO_(2)reduction reaction(CO_(2)RR)is highly promising to convert CO_(2)into economically viable carbon-based chemicals or fuels under mild process conditions.Herein,mesoporous indium supported on multi-walled carbon nanotubes(mp-In@MWCNTs)is synthesized via a facile wet chemical method.The mp-In@MWCNTs electrocatalysts exhibit high CO_(2)RR performance in reducing CO_(2)into formate.An outstanding activity(current density-78.5 mA cm^(-2)),high conversion efficiency(Faradaic efficiency of formate over 90%),and persistent stability(∼30 h)for selective CO_(2)-to-formate conversion are observed.The outstanding CO_(2)RR process performance is attributed to the unique structures with mesoporous surfaces and a conductive network,which promote the adsorption and desorption of reactants and intermediates while improving electron transfer.These findings provide guiding principles for synthesizing conductive metal-based electrocatalysts for high-performance CO_(2)conversion.展开更多
基金financially supported by a PhD Grant from VITO’s Strategic Research Funds(No.2310345).
文摘Electrochemical CO_(2) reduction is a sustainable method for producing fuels and chemicals using renewable energy sources.Sn is a widely employed catalyst for formate production,with its performance closely influenced by the catalyst ink formulations and reac-tion conditions.The present study explores the influence of catalyst loading,current density,and binder choice on Sn-based CO_(2) reduc-tion systems.Decreasing catalyst loading from 10 to 1.685 mg·cm^(-2) and increasing current density in highly concentrated bicarbonate solutions significantly enhances formate selectivity,achieving 88%faradaic efficiency(FE)at a current density of−30 mA·cm^(-2) with a cathodic potential of−1.22 V vs.reversible hydrogen electrode(RHE)and a catalyst loading of 1.685 mg·cm^(-2).This low-loading strategy not only reduces catalyst costs but also enhances surface utilization and suppresses the hydrogen evolution reaction.Nafion enhances formate production when applied as a surface coating rather than pre-mixed in the ink,as evidenced by improved faradaic efficiency and lower cathodic potentials.However,this performance still does not match that of binder-free systems because Sn-based catalysts intrinsic-ally exhibit high catalytic activity,making the binder contribution less significant.Although modifying the electrode surface with binders leads to blocked active sites and increased resistance,polyvinylidene fluoride(PVDF)remains promising because of its stability,strength,and conductivity,achieving up to 72%FE to formate at−30 mA·cm^(-2) and−1.66 V vs.RHE.The findings of this research reveal method-ologies for optimizing the catalyst ink formulations and binder utilization to enhance the conversion of CO_(2) to formate,thereby offering crucial insights for the development of a cost-efficient catalyst for high-current-density operations.
基金the Max Planck Centre for Fundamental Heterogeneous Catalysis(FUNCAT)for financial supportThe authors acknowledge funding from the National Natural Science Foundation of China(No.22002131)China Postdoctoral Science Foundation(No.2020M671963)。
文摘CO_(2)electrolysis into formate is a promising technology with the potential to simultaneously alleviate energy shortages and global warming.However,the limited stability of the catalysts during long-term electrolysis hinders their widespread implementation.Herein,we show that a core-shell bimetallic BiAg catalyst with a multifaceted Janus structure at its core can achieve a stability of up to 300 h with a formate faradaic efficiency(FE_(formate))over 90%at−0.75 V vs.RHE(reversible hydrogen electrode)in an H-type cell.Our investigations reveal the important role of the Janus structure on the transfer of electrons,favoring their delocalization across the catalyst and enhancing their mobility.We propose that the compressive strain inclined to grain boundaries within this structure would lower the energy barrier for electrons transfer and promotes the cooperation between Ag and Bi.Indeed,Ag initiates the activation of CO_(2)through a series of cascade reactions and is subsequently hydrogenated on Bi.Additionally,our study suggests that Ag plays a crucial role in stabilizing the catalyst structure after long-term electrolysis.This work highlights a new strategy for tandem CO_(2)electrolysis,providing novel insights for the design of formate formation catalysts.
基金support by the Natural Science Foundation of Jiangsu Province(BK20210867,BK20231342)the China Postdoctoral Science Foundation(2024M752349)+1 种基金National Natural Science Foundation of China(U1604121)the Doctor Project of Mass Entrepreneurship and Innovation in Jiangsu Province.
文摘CO2 hydrogenation to formate is an effective strategy for promoting the sustainable carbon cycle.However,formate yields are significantly influenced by the amount of noble metal(e.g.,Pd)used.Here,we present Pd-Ni synergistic catalysis on the hollow NiCo2O4 spinel arrays(PdxNiy/NCO@CC)for enhanced formate production under mild conditions.The Pd-Ni dual-site structure effectively enhances electron accumulation on Pd via charge polarization and the synergistic interaction between Pd and Ni,leading to significantly improved formate yields with a reduced usage of noble metal catalyst.The optimized Pd5Ni5/NCO@CC catalyst achieved a remarkable formate yield of 282.5 molformate molPd^(-1)h^(-1)at 333 K and demonstrated high stability.This strategy of synergistically enhancing catalytic activity via bimetallic sites highlights its advantages in other catalytic fields and practical applications.
基金supported by the National Key Research and Development Program of China(No.2018YFB1501405)the National Natural Science Foundation of China(No.52476185).
文摘SnS has emerged as an attractive catalyst for the electrochemical CO_(2)reduction reaction(CO_(2)RR)to formate,while its long-term operational stability is hindered by the self-reduction of Sn^(2+) and sulfur dissolution.Thus,maintaining high current efficiency across a wide negative potential range to achieve high production rates of formate remains a significant challenge.In this study,we present a heterostructure constructed with SnS and CuS for efficient CO_(2)RR to formate.The SnS-CuS(30)exhibits a remarkable formate Faradaic efficiency(FE_(f))of 93.94%at−1 V vs.reversible hydrogen electrode(RHE)and demonstrates long-term stability for 7.5 h,maintaining high activity(with an average FE_(f)of 85.6%)across a wide negative potential range(from-0.8 to-1.2 V(vs.RHE)).The results reveal that the heterogeneous interface between SnS and CuS mitigates the self-reduction issue of SnS by sacrificing Cu^(2+),highlighting that the true active species is SnS,which effectively resists structural changes during the electrolysis process under the protection of CuS.The synergistic interaction within the CuS and SnS heterostructure,combined with the tendency for electron self-conduction,enables the catalyst to maintain high formate activity and selectivity across a wide potential range.Furthermore,theoretical results further indicate that the incorporation of CuS enhances CO_(2)adsorption and lowers the energy barrier for the formation of formate intermediates.This study inspires the concept of applying protective layers to active species,promoting high selectivity in Sn-based electrocatalysts.
基金financially supported by the Shenzhen Science and Technology Project(GXWD20220818163456002)the Key-Area Research and Development Program of Guangdong Province(No.2022B0701180002)+1 种基金the Sauvage Laboratory for Smart Materials of Harbin Institute of Technology(Shenzhen)the Guangdong Province College Students Science and Technology Innovation Cultivation Special Project.
文摘This study investigates using an antioxidation copper particle-free paste,formulated with self-reducing copper formate,for Cu-Cu bonding in electronic packaging applications.The research highlights the oxidation resistance of copper formate compared to traditional copper nanoparticles(CuNPs)and its ability to generate CuNPs through thermal decomposition.Experimental results demonstrate that the sintering process benefits from releasing reductive gases during decomposition,improving joint quality with reduced porosity and enhanced mechanical strength at elevated temperatures.Molecular dynamics simulations further elucidate the sintering behavior of CuNPs,providing significant insights into pore collapse,atomic mobility,and neck formation.The findings indicate that increased temperatures enhance surface and bulk diffusion,facilitating robust particle connections.Overall,this work establishes the potential of copper formate for achieving reliable interconnects in semiconductor devices,paving the way for advancements in material formulations for direct copper–copper bonding.
基金We highly thank the funding from the National Natural Science Foundation of China(grants 22222806,22178162,22072065,and 22408170)the Distinguished Youth Foundation of Jiangsu Province(BK20220053)+2 种基金the National Key Research and Development Program of China(2024YFE0206900)the Six Talent Peaks Project in Jiangsu Province(grant JNHB-035)Agency for Science,Technology and Research(A*STAR)through Low Carbon Energy Research Finding Initiative(LCERFI01-0033|U2102d2006).
文摘Paired electrolysis of waste feedstocks holds an energy-efficient alternative for chemical production;however,the sluggish anodic oxidation limited the total efficiency under larger current density.Herein,we constructed ultralow-coordinated Ni species with Ni–O coordination number of∼3 via a hydrothermal synthesis-sulfidation-annealing process and electrochemical activation and demonstrated the vital role in accelerating the proton deintercalation and reactive oxygen intermediate·OH formation during electro-reforming polyethylene terephthalate hydrolysate(POR).The target catalyst NiCoSx/NF afforded a high formate productivity of 7.4 mmol cm^(−2)h^(−1)at∼600 mA cm^(−2)with a formate Faradic efficiency(FE_(formate))of 92.4%in POR and maintained a FE_(formate)of∼90%for 100 h at 2 A in a membrane electrode assembly electrolyzer.Coupling POR on NiCoSx/NF with carbon dioxide reduction reaction on oxygen vacancies enriched Vo-BiSnO reached effective concurrent formate production with 172.7%of FE_(formate)at 500 mA cm^(−2)and long-term stability.Such excellent performance shows the great prospect of electrocatalyst design by regulating the local metal environment.
基金supported by the National Natural Science Foundation of China(Nos.22172099,U21A20312)Guangdong Basic and Applied Basic Research Foundation(Nos.2023A1515012776,2022B1515120084)the Shenzhen Science and Technology Program(No.RCYX20200714114535052)。
文摘Leveraging the interplay between the metal component and the supporting material represents a cornerstone strategy for augmenting electrocatalytic efficiency,e.g.,electrocatalytic CO_(2)reduction reaction(CO_(2)RR).Herein,we employ freestanding porous carbon fibers(PCNF)as an efficacious and stable support for the uniformly distributed SnO_(2)nanoparticles(SnO_(2)PCNF),thereby capitalizing on the synergistic support effect that arises from their strong interaction.On one hand,the interaction between the SnO_(2)nanoparticles and the carbon support optimizes the electronic configuration of the active centers.This interaction leads to a noteworthy shift of the d-band center toward stronger intermediate adsorption energy,consequently lowering the energy barrier associated with CO_(2)reduction.As a result,the Sn O_(2)PCNF realizes a remarkable CO_(2)RR performance with excellent selectivity towards formate(98.1%).On the other hand,the porous carbon fibers enable the uniform and stable dispersion of SnO_(2)nanoparticles,and this superior porous structure of carbon supports can also facilitate the exposure of the SnO_(2)nanoparticles on the reaction interface to a great extent.Consequently,adequate contact between active sites,reactants,and electrolytes can significantly increase the metal utilization,eventually bringing forth a remarkable7.09 A/mg mass activity.This work might provide a useful idea for improving the utilization rate of metals in numerous electrocatalytic reactions.
基金Project(52204378)supported by the National Natural Science Foundation of China。
文摘The selective reduction of carbon dioxide(CO_(2))into high-value-added chemicals is one of the most effective means to solve the current energy and environmental problems,which could realize the utilization of CO_(2) and promote the balance of the carbon cycle.Formate is one of the most economical and practical products of all the electrochemical CO_(2) reduction products.Among the many metal-based electrocatalysts that can convert CO_(2) into formate,Sn-based catalysts have received a lot of attention because of their low-cost,non-toxic characteristics and high selectivity for formate.In this article,the most recent development of Sn-based electrocatalysts is comprehensively summarized by giving examples,which are mainly divided into monometallic Sn,alloyed Sn,Sn-based compounds and Sn composite catalysts.Finally,the current performance enhancement strategies and future directions of the field are summarized.
基金financially supported by the Fundamental Research Funds for the Central Universities of Central South University(No.2022ZZTS0579).
文摘The large current density of electrochemical CO_(2)reduction towards industrial application is challenging.Herein,without strong acid and reductant,the synthesized BiVO_(4)with abundant oxygen vacancies(Ovs)exhibited a high formate Faradaic efficiency(FE)of 97.45%(-0.9 V)and a large partial current density of-45.82 mA/cm^(2)(-1.2 V).The good performance benefits from the reconstruction of BiVO_(4)to generate active metal Bi sites,which results in the electron redistribution to boost the OCHO∗formation.In flow cells,near industrial current density of 183.94 mA/cm^(2)was achieved,with the FE of formate above 95%from 20mA/cm^(2)to 180mA/cm^(2).Our work provides a facily synthesized BiVO_(4)precatalyst for CO_(2)electroreduction.
文摘The p-block metal(In,Sn,Bi,etc.)-based electrocatalysts have exhibited excellent activity in the electrocatalytic CO_(2)reduction(ECR)to formate.However,the rapid decrease in catalytic activity caused by catalyst reconstruction and agglomeration under ECR conditions significantly restricts their practical applications.Herein,we developed a sulfur anchoring strategy to stabilize the high-density sub-3 nm In_(2)S_(3)nanoparticles on sulfur-doped porous carbon substrates(i-In_(2)S_(3)/S-C)for formate production.Systematic characterizations evidenced that the as-prepared catalyst exhibited a strong metal sulfide-support interaction(MSSI),which effectively regulated the electronic states of In_(2)S_(3),achieving a high formate Faradaic efficiency of 91%at−0.95 V vs.RHE.More importantly,the sulfur anchoring effectively immobilized the sub-3 nm In_(2)S_(3)nanoparticles to prevent them from agglomeration.It enabled the catalysts to exhibit much higher durability than the In_(2)S_(3)samples without sulfur anchoring,demonstrating that the strong MSSI and fast charge transfer on the catalytic interface could significantly promote the structural stability of In_(2)S_(3)catalysts.These results provide a viable approach for developing efficient and stable electrocatalysts for CO_(2)reduction.
基金financial support from the National Natural Science Foundation of China(Nos.22271024,21632005)Changzhou University.
文摘Double bonds of internal olefins can be efficiently migrated to the terminal carbons and regioselectively hydroesterified with formates in the presence of Pd(OAc)_(2) and 1,2-DTBPMB under mild reaction conditions,providing a wide variety of corresponding linear carboxylic esters bearing various functional groups in good yields and>20:1 linear/branch ratios.The reaction is optionally simple and does not need to use CO gas and acid co-catalysts.
基金supported by the National Natural Science Foundation of China(Nos.22276064 and 22278168)the Open Research Fund of Academy of Advanced Carbon Conversion Technology of Huaqiao University(No.AACCT0003)the Science and Technology Project of Fujian province(No.2022Y3007).
文摘The electrocatalytic reduction of carbon dioxide(CO_(2)ER)into formate presents a compelling solution for mitigating dependence on fossil energy and green utilization of CO_(2).Bismuth(Bi)has been gaining recognition as a promising catalyst material for the CO_(2)ER to formate.The performance of Bi catalysts(named as Bi-V)can be significantly improved when they possess single metal atom vacancy.However,creating larger-sized metal atom vacancies within Bi catalysts remains a significant challenge.In this work,Bi nanosheets with dual V0 Bi vacancy(Bi-DV)were synthesized utilizing in situ electrochemical transformation,using BiOBr nanosheets with triple vacancy associates(V■_(Bi)V··_(O)V■_(Bi),V■_(Bi)and V··_(O)denote the Bi^(3+)and O_(2)−vacancy,respectively)as a template.The obtained Bi-DV achieved higher CO_(2)ER activity than Bi-V,showing Faradaic efficiency for formate production of>92%from-0.9 to-1.2 VRHE in an H-type cell,and the partial current density of formate reached up to 755 mA/cm^(2)in a flow cell.The comprehensive characterizations coupled with density functional theory calculations demonstrate that the dual V^(0)_(Bi)vacancy on the surface of Bi-DV expedite the reaction kinetics toward CO_(2)ER,by reducing the thermodynamic barrier of^(∗)OCHO intermediate formation.This research provides critical insights into the potential of large atom vacancies to enhance electrocatalysis performance.
基金financially supported by the National Natural Science Foundation of China(Nos.22072110 and 21872107)the Key Research and Development Projects of Hubei Province,China(2022BAA083)。
文摘CO_(2) electrochemical reduction(CO_(2)ER)is an important research area for carbon neutralization.However,available catalysts for CO_(2) reduction are still characterized by limited stability and activity.Recently,metallic bismuth(Bi)has emerged as a promising catalyst for CO_(2) ER.Herein,we report the solid cathode electroreduction of commercial micronized Bi2O3as a straightforward approach for the preparation of nanostructured Bi.At-1.1 V versus reversible hydrogen electrode in a KHCO3aqueous electrolyte,the resulting nanostructure Bi delivers a formate current density of~40 mA·cm^(-2) with a current efficiency of~86%,and the formate selectivity reaches97.6% at-0.78 V.Using nanosized Bi2O3as the precursor can further reduce the primary particle sizes of the resulting Bi,leading to a significantly increased formate selectivity at relatively low overpotentials.The high catalytic activity of nanostructured Bi is attributable to the ultrafine and interconnected Bi nanoparticles in the nanoporous structure,which exposes abundant active sites for CO_(2) electrocatalytic reduction.
基金financially supported by the National Natural Science Foundation of China(22072087)。
文摘Electro-reduction of carbon dioxide(ERCO_(2)) is considered an effective method to alleviate the greenhouse effect and produce value-added chemicals.Achieving the dominant selectivity of Zn-based catalysts for formate remains a challenge.In this article,the ZnIn-E_(12) catalyst is successfully prepared by solvent assisted ligand exchange(SALE) method to convert organic ligands,achieving a Faradaic efficiency of 72.28% for formate at-1.26 V vs.RHE(V_(RHE)),which is 1.42 times higher than the original catalyst.Evidence shows that the successful conversion of organic ligands can transform the catalyst from the original large size polyhedron to cross-linked network of particles with a diameter of about 30 nm.The increased specific surface area can expose more active sites and facilitate the electrocatalytic conversion of CO_(2) to formate.This work is expected to provide inspiration for the regulation of formate selectivity and catalyst size in Zn-based catalysts.
基金supported by the Youth Program of the National Natural Science Foundation of China(No.52001061)the Young Elite Scientist Sponsorship Program Cast(No.YESS20200139)the Fundamental Research Funds for the Central Universities(No.N2202016).
文摘The corrosion and passive behavior of HP-13Cr stainless steel(HP-13Cr SS)in formate annulus protection fluid was investigated.HP-13Cr SS exhibited good passive behavior in clean formate annulus protection fluid,which was attributed to a thinner and more dense passive film mainly composed of Cr_(2)O_(3).In the formation water solution,the passive film was composed of metastable Cr(OH)3,which was explained by the isoelectric point theory,resulting in the deterioration of the passive behavior of HP-13Cr SS.When the formation water penetrated the formate annulus protection fluid,a large number of loose FeCO_(3)particles formed in the corrosion scales,thus HP-13Cr SS suffered severe corrosion.Therefore,avoiding formation water penetrating the formate annulus protection fluid is conducive to improving the service life of HP-13Cr SS oil tubes in extremely aggressive environment.
基金financially supported by the National Natural Science Foundation of China(52072409)the Major Scientific and Technological Innovation Project of Shandong Province(2020CXGC010403)+1 种基金the Taishan Scholar Project(No.ts201712020)the Natural Science Foundation of Shandong Province(ZR2021QE062)
文摘CO_(2)electrochemical reduction reaction(CO_(2)RR)to formate is a hopeful pathway for reducing CO_(2)and producing high-value chemicals,which needs highly selective catalysts with ultra-broad potential windows to meet the industrial demands.Herein,the nanorod-like bimetallic ln_(2)O_(3)/Bi_(2)O_(3)catalysts were successfully synthesized by pyrolysis of bimetallic InBi-MOF precursors.The abundant oxygen vacancies generated from the lattice mismatch of Bi_(2)O_(3)and ln_(2)O_(3)reduced the activation energy of CO_(2)to*CO_(2)·^(-)and improved the selectivity of*CO_(2)·^(-)to formate simultaneously.Meanwhile,the carbon skeleton derived from the pyrolysis of organic framework of InBi-MOF provided a conductive network to accelerate the electrons transmission.The catalyst exhibited an ultra-broad applied potential window of 1200 mV(from-0.4 to-1.6 V vs RHE),relativistic high Faradaic efficiency of formate(99.92%)and satisfactory stability after 30 h.The in situ FT-IR experiment and DFT calculation verified that the abundant oxygen vacancies on the surface of catalysts can easily absorb CO_(2)molecules,and oxygen vacancy path is dominant pathway.This work provides a convenient method to construct high-performance bimetallic catalysts for the industrial application of CO_(2)RR.
基金supported by the National Natural Science Foundation of China(22238013 and 22178393)Postdoctoral Science Foundation of Central South University(320808)+1 种基金Natural Science Foundation of Hunan Province(2023JJ40706)the High Performance Computing Center of Central South University。
文摘CO_(2)-to-formate electrosynthesis with high selectivity and stability has been a long-sought objective.Unfortunately,most catalysts undergo structural and valence state changes due to surface oxidation during operation or storage,resulting in decreased catalytic performance.Herein,we report a efficient and stable BiIn@Cu-foam electrode through the in-situ regeneration of Bi^(0) active sites to renew the surface activation.The electronic structure of Bi site can be regulated by introducing In,thereby enhancing the adsorption strength of*OCHO.The optimized electrode exhibits over 90%FE_(formate)at a wide potential window(-0.9–-2.2 V),and formation rate for 3.15 mM cm^(-1)h^(-1).Especially,the electrode can maintain the high performance at continuously electrolysis for more than 300 h,or for more than 50 cycles,even repeated operation and storage for more than 2 years.This work provides a promising candidate and new insight to construct industrially viable stable Bi-based catalyst for formate electrosynthesis.
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.
文摘An efficient and sustainable protocol for regioselective hydrocarboxylation of alkynes to construct diverse propionic acid derivatives is disclosed.Under photoinduced conditions,the anti-Markovnikov hydrocarboxylation of alkynes was realized with CO_(2) radical anion in-situ generated from formate as both a carbonyl source and a reductant.The collaboration between photosensitizer and hydrogen atom transfer catalyst promoted the catalytic cycle to work smoothly,giving a broad substrate scope including terminal and internal alkynes.The Giese radical addition of CO_(2) radical anion to the C—C triple bond is the key step to initiate the reaction.
基金Jiujiang Research Institute in Xiamen University for the partial supportthe support of QUT Faculty Centre Strategic Funding provided by the Faculty of Science and QUT Centre for a Waste-Free World+1 种基金the Australian Research Council(ARC)QUT Centre for Materials Science for partial support
文摘Ever-increasing emissions of anthropogenic carbon dioxide(CO_(2))cause global environmental and climate challenges.Inspired by biological photosynthesis,developing effective strategies NeuNlto up-cycle CO_(2)into high-value organics is crucial.Electrochemical CO_(2)reduction reaction(CO_(2)RR)is highly promising to convert CO_(2)into economically viable carbon-based chemicals or fuels under mild process conditions.Herein,mesoporous indium supported on multi-walled carbon nanotubes(mp-In@MWCNTs)is synthesized via a facile wet chemical method.The mp-In@MWCNTs electrocatalysts exhibit high CO_(2)RR performance in reducing CO_(2)into formate.An outstanding activity(current density-78.5 mA cm^(-2)),high conversion efficiency(Faradaic efficiency of formate over 90%),and persistent stability(∼30 h)for selective CO_(2)-to-formate conversion are observed.The outstanding CO_(2)RR process performance is attributed to the unique structures with mesoporous surfaces and a conductive network,which promote the adsorption and desorption of reactants and intermediates while improving electron transfer.These findings provide guiding principles for synthesizing conductive metal-based electrocatalysts for high-performance CO_(2)conversion.
