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
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
CO_(2) 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 s...CO_(2) 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 NiCo_(2)O_(4) spinel arrays(Pd_(x)Ni_(y)/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 Pd_(5)Ni_(5)/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
Achieving industrial-level electrochemical CO_(2)reduction to formate remains a significant challenge due to limitations in catalyst selectivity and interfacial proton management at high current densities.In a recent ...Achieving industrial-level electrochemical CO_(2)reduction to formate remains a significant challenge due to limitations in catalyst selectivity and interfacial proton management at high current densities.In a recent study,Prof.Guo and colleagues report the development of Turingstructured electrocatalysts,which incorporate reaction-diffusion-inspired topologies to engineer mesoscale surface patterns.This design enables precise modulation of the interfacial microenvironment,enhancing CO_(2)activation and suppressing competing hydrogen evolution.The resulting catalysts achieve efficient and stable CO_(2)-to-formate conversion under industrially relevant conditions,offering a promising strategy for scalable carbon-neutral chemical production.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
The mechanism and kinetics of electrocatalytic oxidation of formic acid at Pt electrodes is discussed in detail based on previous electrochemical in-situ ATR-FTIRS data [Langmuir 22, 10399 （2006）and Angewa. Chem. In...The mechanism and kinetics of electrocatalytic oxidation of formic acid at Pt electrodes is discussed in detail based on previous electrochemical in-situ ATR-FTIRS data [Langmuir 22, 10399 （2006）and Angewa. Chem. Int. Ed. 50, 1159 （2011）]. A kinetic model with formic acid adsorption （and probably the simultaneous C-H bond activation） as the rate determining step, which contributes to the majority of reaction current for formic acid oxi- dation, was proposed for the direct pathway. The model simulates well the IR spectroscopic results obtained under conditions where the poisoning effect of carbon monoxide （CO） is negligible and formic acid concentration is below 0.1 mol/L. The kinetic simulation predicts that in the direct pathway formic acid oxidation probably only needs one Pt atom as active site, formate is the site blocking species instead of being the active intermediate. We review in detail the conclusion that formate pathway （with either 1st or 2nd order reaction kinetics） is the direct pathway, possible origins for the discrepancies are pointed out.展开更多
Fast scan voltammetry is an efficient tool to distinguish oxidative/reductive adsorp- tion/desorption from that for bulk reaction. In this work, we provide a methodology that the isotherm of oxidative/reductive adsorp...Fast scan voltammetry is an efficient tool to distinguish oxidative/reductive adsorp- tion/desorption from that for bulk reaction. In this work, we provide a methodology that the isotherm of oxidative/reductive adsorption desorption processes at electrode surface can be obtained using just one solution with relatively low reactant concentration, by taking the advantage of varying the potential scan rate （relative of the diffusion rate） to tune the adsorption rate and proper mathematic treatment. The methodology is demonstrated by taking acetate adsorption at Pt（lll） in acidic solution as an example. The possibility for extension of this method toward mechanistic studies of complicated electrocatalytic reactions is also given.展开更多
Formic acid （HCOOH） decomposition at Pt film electrode has been studied by electrochem- ical in situ FTIR spectroscopy under attenuated-total-reflection configuration, in order to clarify whether bridge-bonded forma...Formic acid （HCOOH） decomposition at Pt film electrode has been studied by electrochem- ical in situ FTIR spectroscopy under attenuated-total-reflection configuration, in order to clarify whether bridge-bonded formate （HCOOD） is the reactive intermediate for COad for-mation from HCOOH molecules. When switching from HCOOH-free solution to HCOOH- containing solution at constant potential （E=0.4 V vs. RHE）, we found that immediately upon solution switch COad formation rate is the highest, while surface coverage of formate is zero, then after COad formation rate decreases, while formate coverage reaches a steady state coverage quickly within ca. 1 s. Potential step experiment from E=0.75 V to 0.35 V, reveals that formate band intensity drops immediately right after the potential step, while the COad signal develops slowly with time. Both facts indicate that formate is not the reactive intermediate for formic acid dehydration to CO.展开更多
Energy-saving glycerol electrolysis with lower potential than water spitting endows a promising way for the concurrent production of value-added formate and high-purity hydrogen. However, there is still lack of effici...Energy-saving glycerol electrolysis with lower potential than water spitting endows a promising way for the concurrent production of value-added formate and high-purity hydrogen. However, there is still lack of efficient electrocatalysts at both anode and cathode for glycerol electrolysis. Herein, we report the activation of Ni site in NiV layered double hydroxide(LDH) by electrochemical and N_(2)/H_(2) plasma regulations for boosting the activity of glycerol oxidation reaction(GOR) and hydrogen evolution reaction(HER), respectively. Specifically, boosted GOR performance with a low overpotential(1.23 V at 10 mA·cm^(-2)) and a high Faradic efficiency(94%) is demonstrated by electrochemically regulated NiV LDH(ENiV LDH) with elevated valence state of Ni site. In situ Raman spectrum reveals the generation of Ni(Ⅲ) species by electrochemical regulation, and the highly active Ni(Ⅲ)can be regenerated with the process of electrochemical oxidation. Additionally, the possible reaction pathway is speculated based on the in situ Fourier transform infrared spectroscopy(FTIR) and high-performance liquid chromatography results. The plasma-regulated NiV LDH(PNiV LDH) with lower valence state of Ni site exhibits outstanding HER activity, displaying a low overpotential of 45 m V to deliver 10 mA·cm^(-2).When employing E-NiV LDH and P-NiV LDH as anode and cathode electrocatalyst, respectively, the assembled electrolyzer merely needs 1.25 V to achieve 10 m A·cm^(-2) for simultaneous production of formate and hydrogen, demonstrating remarkable 320 mV of lower potential than water electrolysis.展开更多
Selective CO_(2) reduction to formate with highadded value is one of the most technologically and economically feasible pathways to realize electrochemical CO_(2) fixation. Bismuth-based catalysts have the advantages ...Selective CO_(2) reduction to formate with highadded value is one of the most technologically and economically feasible pathways to realize electrochemical CO_(2) fixation. Bismuth-based catalysts have the advantages of nontoxicity, low cost, high abundance, as well as excellent stability. In addition, bismuth-based catalysts display excellent selectivity for the electrochemical reduction of CO_(2) to formate in aqueous electrolytes due to high-hydrogen evolution overpotential. Hence, bismuthbased catalysts are by far the most commercially available materials for electrochemical reduction of CO_(2) to formate.In this review, the electrochemical reduction of CO_(2) to formate over bismuth-based catalysts is elaborated. Firstly,this review describes performance evaluation indexes,evaluation systems and reaction mechanisms of the electrochemical reduction of CO_(2) to formate over bismuthbased catalysts. Subsequently, the research means to reveal the reaction mechanism of electrochemical reduction of CO_(2) to formate over bismuth-based catalysts and the performance improvement strategies of the reaction are described in detail. Finally, the opportunities and challenges in this encouraging field are discussed. We believe that this review will contribute to further development of electrochemical reduction of CO_(2) to formate over bismuthbased catalysts.展开更多
In this perspective article,the synthesis and thermodynamic properties of aqueous solutions of formate salts(FS,HCO2-)are described in relationship to the concept of H2carriers.The physiochemical properties of solid F...In this perspective article,the synthesis and thermodynamic properties of aqueous solutions of formate salts(FS,HCO2-)are described in relationship to the concept of H2carriers.The physiochemical properties of solid FS,aqueous formate solutions,and aqueous bicarbonate solutions set the limitations for storage capacity,deliverable capacity,and usable H2capacity of these H2carriers,respectively.These parameters will help in the design of systems that use H2carriers for storage and transport of H2for fuel cell power applications.FS,as well as admixtures with formic acid(FA,H2CO2),have potential to address the goals outlined in the U.S.Department of Energy’s H2@scale initiative to store in chemical bonds a significant quantity of energy(hundreds of megawatts)obtained from large scale renewable resources.展开更多
Electrocatalytic CO2 reduction(CO2 ER)into formate is a desirable route to achieve efficient transformation of CO2 to value-added chemicals,however,it still suffers from limited catalytic activity and poor selectivity...Electrocatalytic CO2 reduction(CO2 ER)into formate is a desirable route to achieve efficient transformation of CO2 to value-added chemicals,however,it still suffers from limited catalytic activity and poor selectivity.Herein,we develop a hybrid electrocatalyst composed of bismuth and bismuth oxide nanoparticles(NPs)supported on nitrogen-doped reduced graphene oxide(Bi/Bi2 O3/NrGO)nanosheets prepared by a combined hydrothermal with calcination treatment.Thanks to the combination of undercoordinated sites and strong synergistic effect between Bi and Bi2 O3,Bi/Bi2 O3/NrGO-700 hybrid displays a promoted CO2 ER catalytic performance and selectivity for formate production,as featured by a small onset potential of-0.5 V,a high current density of-18 mA/cm2,the maximum Faradaic efficiency of85%at-0.9 V,and a low Tafel slope of 166 mV/dec.Experimental results reveal that the higher CO2 ER performance of Bi/Bi2 O3/NrGO-700 than that of Bi NPs supported on NrGO(Bi/NrGO)can be due to the partial reduction of Bi2 O3 NPs into Bi,which significantly increases undercoordinated active sites on Bi NPs surface,thus boosting its CO2 ER performance.Furthermore,a two-electrode device with Ir/C anode and Bi/Bi2 O3/NrGO-700 cathode could be integrated with two alkaline batteries or a planar solar cell to achieve highly active water splitting and CO2 ER.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.
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CO_(2) 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 NiCo_(2)O_(4) spinel arrays(Pd_(x)Ni_(y)/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 Pd_(5)Ni_(5)/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financially supported by the National Natural Science Foundation of China(No.22209024)Tongcheng R&D Foundation(No.CPCIF-RA-0102)the State Key Laboratory of Advanced Fiber Materials,Donghua University
文摘Achieving industrial-level electrochemical CO_(2)reduction to formate remains a significant challenge due to limitations in catalyst selectivity and interfacial proton management at high current densities.In a recent study,Prof.Guo and colleagues report the development of Turingstructured electrocatalysts,which incorporate reaction-diffusion-inspired topologies to engineer mesoscale surface patterns.This design enables precise modulation of the interfacial microenvironment,enhancing CO_(2)activation and suppressing competing hydrogen evolution.The resulting catalysts achieve efficient and stable CO_(2)-to-formate conversion under industrially relevant conditions,offering a promising strategy for scalable carbon-neutral chemical production.
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This work was supported by one hundred Tal- ents＇ Program of the Chinese Academy of Science, the National Natural Science Foundation of China （No.21273215）, 973 program from the Ministry of Sci- ence and Technology of China （No.2010CB923302）.
文摘The mechanism and kinetics of electrocatalytic oxidation of formic acid at Pt electrodes is discussed in detail based on previous electrochemical in-situ ATR-FTIRS data [Langmuir 22, 10399 （2006）and Angewa. Chem. Int. Ed. 50, 1159 （2011）]. A kinetic model with formic acid adsorption （and probably the simultaneous C-H bond activation） as the rate determining step, which contributes to the majority of reaction current for formic acid oxi- dation, was proposed for the direct pathway. The model simulates well the IR spectroscopic results obtained under conditions where the poisoning effect of carbon monoxide （CO） is negligible and formic acid concentration is below 0.1 mol/L. The kinetic simulation predicts that in the direct pathway formic acid oxidation probably only needs one Pt atom as active site, formate is the site blocking species instead of being the active intermediate. We review in detail the conclusion that formate pathway （with either 1st or 2nd order reaction kinetics） is the direct pathway, possible origins for the discrepancies are pointed out.
基金This work was supported by one Hundred Talents＇ Program of the Chinese Academy of Science, the National Natural Science Foundation of China （No.20773116, No.21273215, and No.J1030412）, and 973 Program from theMinistry of Science and Technology of China （No.2010CB923302）. Many Thanks to Prof. Shen Ye from Hokkaido university for the help in establishing techniques for single crystalline electro- chemistry.
文摘Fast scan voltammetry is an efficient tool to distinguish oxidative/reductive adsorp- tion/desorption from that for bulk reaction. In this work, we provide a methodology that the isotherm of oxidative/reductive adsorption desorption processes at electrode surface can be obtained using just one solution with relatively low reactant concentration, by taking the advantage of varying the potential scan rate （relative of the diffusion rate） to tune the adsorption rate and proper mathematic treatment. The methodology is demonstrated by taking acetate adsorption at Pt（lll） in acidic solution as an example. The possibility for extension of this method toward mechanistic studies of complicated electrocatalytic reactions is also given.
文摘Formic acid （HCOOH） decomposition at Pt film electrode has been studied by electrochem- ical in situ FTIR spectroscopy under attenuated-total-reflection configuration, in order to clarify whether bridge-bonded formate （HCOOD） is the reactive intermediate for COad for-mation from HCOOH molecules. When switching from HCOOH-free solution to HCOOH- containing solution at constant potential （E=0.4 V vs. RHE）, we found that immediately upon solution switch COad formation rate is the highest, while surface coverage of formate is zero, then after COad formation rate decreases, while formate coverage reaches a steady state coverage quickly within ca. 1 s. Potential step experiment from E=0.75 V to 0.35 V, reveals that formate band intensity drops immediately right after the potential step, while the COad signal develops slowly with time. Both facts indicate that formate is not the reactive intermediate for formic acid dehydration to CO.
基金the National Science Foundation of China(No.12075002)the Outstanding Youth Fund of Anhui Province(No.2008085J21)+1 种基金Anhui Provincial Supporting Program for Excellent Young Talents in Universities(No.gxyqZD2019005)the Innovation and Entrepreneurship Project of Overseas Returnees in Anhui Province(No.2019LCX018)。
文摘Energy-saving glycerol electrolysis with lower potential than water spitting endows a promising way for the concurrent production of value-added formate and high-purity hydrogen. However, there is still lack of efficient electrocatalysts at both anode and cathode for glycerol electrolysis. Herein, we report the activation of Ni site in NiV layered double hydroxide(LDH) by electrochemical and N_(2)/H_(2) plasma regulations for boosting the activity of glycerol oxidation reaction(GOR) and hydrogen evolution reaction(HER), respectively. Specifically, boosted GOR performance with a low overpotential(1.23 V at 10 mA·cm^(-2)) and a high Faradic efficiency(94%) is demonstrated by electrochemically regulated NiV LDH(ENiV LDH) with elevated valence state of Ni site. In situ Raman spectrum reveals the generation of Ni(Ⅲ) species by electrochemical regulation, and the highly active Ni(Ⅲ)can be regenerated with the process of electrochemical oxidation. Additionally, the possible reaction pathway is speculated based on the in situ Fourier transform infrared spectroscopy(FTIR) and high-performance liquid chromatography results. The plasma-regulated NiV LDH(PNiV LDH) with lower valence state of Ni site exhibits outstanding HER activity, displaying a low overpotential of 45 m V to deliver 10 mA·cm^(-2).When employing E-NiV LDH and P-NiV LDH as anode and cathode electrocatalyst, respectively, the assembled electrolyzer merely needs 1.25 V to achieve 10 m A·cm^(-2) for simultaneous production of formate and hydrogen, demonstrating remarkable 320 mV of lower potential than water electrolysis.
基金financially supported by Beijing Natural Science Foundation(No.2204100)the National Natural Science Foundation of China(No.22002185)+2 种基金the Civil Aerospace Technology Research Project(No.B0108)Qian Xuesen Youth Innovation Foundation,the Central Universities(Nos.31020195C001,310201QD0410 and 3102019ZD0403)the Natural Science Foundation of Shaanxi(No.2020JQ-143)。
文摘Selective CO_(2) reduction to formate with highadded value is one of the most technologically and economically feasible pathways to realize electrochemical CO_(2) fixation. Bismuth-based catalysts have the advantages of nontoxicity, low cost, high abundance, as well as excellent stability. In addition, bismuth-based catalysts display excellent selectivity for the electrochemical reduction of CO_(2) to formate in aqueous electrolytes due to high-hydrogen evolution overpotential. Hence, bismuthbased catalysts are by far the most commercially available materials for electrochemical reduction of CO_(2) to formate.In this review, the electrochemical reduction of CO_(2) to formate over bismuth-based catalysts is elaborated. Firstly,this review describes performance evaluation indexes,evaluation systems and reaction mechanisms of the electrochemical reduction of CO_(2) to formate over bismuthbased catalysts. Subsequently, the research means to reveal the reaction mechanism of electrochemical reduction of CO_(2) to formate over bismuth-based catalysts and the performance improvement strategies of the reaction are described in detail. Finally, the opportunities and challenges in this encouraging field are discussed. We believe that this review will contribute to further development of electrochemical reduction of CO_(2) to formate over bismuthbased catalysts.
基金support from the Hydrogen Materials-Advanced Research Consortium(HyMARC)supported by the National Research Foundation(NRF)of Korea grant funded by the Ministry of Science and ICT(2015M1A2A2074688)KIST institutional program funded by the Korea Institute of Science and Technology(2E29610)。
文摘In this perspective article,the synthesis and thermodynamic properties of aqueous solutions of formate salts(FS,HCO2-)are described in relationship to the concept of H2carriers.The physiochemical properties of solid FS,aqueous formate solutions,and aqueous bicarbonate solutions set the limitations for storage capacity,deliverable capacity,and usable H2capacity of these H2carriers,respectively.These parameters will help in the design of systems that use H2carriers for storage and transport of H2for fuel cell power applications.FS,as well as admixtures with formic acid(FA,H2CO2),have potential to address the goals outlined in the U.S.Department of Energy’s H2@scale initiative to store in chemical bonds a significant quantity of energy(hundreds of megawatts)obtained from large scale renewable resources.
基金support of the Natural Science Foundation of Zhejiang Province(No.LR16E080003)support of National Natural Science Foundation of China(Nos.21922811,51702284,21878270)+2 种基金Zhejiang Provincial Natural Science Foundation of China(No.LR19B060002)the Fundamental Research Funds for the Central Universitiesthe Startup Foundation for Hundred-Talent Program of Zhejiang University。
文摘Electrocatalytic CO2 reduction(CO2 ER)into formate is a desirable route to achieve efficient transformation of CO2 to value-added chemicals,however,it still suffers from limited catalytic activity and poor selectivity.Herein,we develop a hybrid electrocatalyst composed of bismuth and bismuth oxide nanoparticles(NPs)supported on nitrogen-doped reduced graphene oxide(Bi/Bi2 O3/NrGO)nanosheets prepared by a combined hydrothermal with calcination treatment.Thanks to the combination of undercoordinated sites and strong synergistic effect between Bi and Bi2 O3,Bi/Bi2 O3/NrGO-700 hybrid displays a promoted CO2 ER catalytic performance and selectivity for formate production,as featured by a small onset potential of-0.5 V,a high current density of-18 mA/cm2,the maximum Faradaic efficiency of85%at-0.9 V,and a low Tafel slope of 166 mV/dec.Experimental results reveal that the higher CO2 ER performance of Bi/Bi2 O3/NrGO-700 than that of Bi NPs supported on NrGO(Bi/NrGO)can be due to the partial reduction of Bi2 O3 NPs into Bi,which significantly increases undercoordinated active sites on Bi NPs surface,thus boosting its CO2 ER performance.Furthermore,a two-electrode device with Ir/C anode and Bi/Bi2 O3/NrGO-700 cathode could be integrated with two alkaline batteries or a planar solar cell to achieve highly active water splitting and CO2 ER.
