Cu-based materials for electrocatalytic CO_(2) to alcohols:Reaction mechanism,catalyst categories,and regulation strategies

Electrocatalytic CO_(2) reduction reaction(CO_(2)RR)technology,which enables carbon capture storage and resource utilization by reducing CO_(2) to valuable chemicals or fuels,has become a global research hotspot in recent decades.Among the many products of CO_(2)RR(carbon monoxide,acids,aldehydes and alcohols,olefins,etc.),alcohols(methanol,ethanol,propanol,etc.)have a higher market value and energy density,but it is also more difficult to produce.Copper is known to be effective in catalyzing CO_(2) to high valueadded alcohols,but with poor selectivity.The progress of Cu-based catalysts for the selective generation of alcohols,including copper oxides,bimetals,single atoms and composites is reviewed.Meanwhile,to improve Cu-based catalyst activity and modulate product selectivity,the modulation strategies are straighten out,including morphological regulation,crystalline surface,oxidation state,as well as elemental doping and defect engineering.Based on the research progress of electrocatalytic CO_(2) reduction for alcohol production on Cu-based materials,the reaction pathways and the key intermediates of the electrocatalytic CO_(2)RR to methanol,ethanol and propanol are summarized.Finally,the problems of traditional electrocatalytic CO_(2)RR are introduced,and the future applications of machine learning and theoretical calculations are prospected.An in-depth discussion and a comprehensive review of the reaction mechanism,catalyst types and regulation strategies were carried out with a view to promoting the development of electrocatalytic CO_(2)RR to alcohols.

Atomic Dispersed Hetero‑Pairs for Enhanced Electrocatalytic CO_(2)Reduction

Electrochemical carbon dioxide reduction reaction(CO_(2)RR)involves a variety of intermediates with highly correlated reaction and ad-desorption energies,hindering optimization of the catalytic activity.For example,increasing the binding of the*COOH to the active site will generally increase the*CO desorption energy.Breaking this relationship may be expected to dramatically improve the intrinsic activity of CO_(2)RR,but remains an unsolved challenge.Herein,we addressed this conundrum by constructing a unique atomic dispersed hetero-pair consisting of Mo-Fe di-atoms anchored on N-doped carbon carrier.This system shows an unprecedented CO_(2)RR intrinsic activity with TOF of 3336 h−1,high selectivity toward CO production,Faradaic efficiency of 95.96%at−0.60 V and excellent stability.Theoretical calculations show that the Mo-Fe diatomic sites increased the*COOH intermediate adsorption energy by bridging adsorption of*COOH intermediates.At the same time,d-d orbital coupling in the Mo-Fe di-atom results in electron delocalization and facilitates desorption of*CO intermediates.Thus,the undesirable correlation between these steps is broken.This work provides a promising approach,specifically the use of di-atoms,for breaking unfavorable relationships based on understanding of the catalytic mechanisms at the atomic scale.

Effects of surface chlorine atoms on charge distribution and reaction barriers for photocatalytic CO_(2)reduction

Photocatalytic CO_(2)reduction to produce high value-added carbon-based fuel has been proposed as a promising approach to mitigate global warming issues.However,the conversion efficiency and product selectivity are still low due to the sluggish dynamics of transfer processes involved in proton-assisted multi-electron reactions.Lowering the formation energy barriers of intermediate products is an effective method to enhance the selectivity and productivity of final products.In this study,we aim to regulate the surface electronic structure of Bi_(2)WO_(6)by doping surface chlorine atoms to achieve effective photocatalytic CO_(2)reduction.Surface Cl atoms can enhance the absorption ability of light,affect its energy band structure and promote charge separation.Combined with DFT calculations,it is revealed that surface Cl atoms can not only change the surface charge distribution which affects the competitive adsorption of H_(2)O and CO_(2),but also lower the formation energy barrier of intermediate products to generate more intermediate*COOH,thus facilitating CO production.Overall,this study demonstrates a promising surface halogenation strategy to enhance the photocatalytic CO_(2)reduction activity of a layered structure Bi-based catalyst.

Recent Advances in Interface Engineering for Electrocatalytic CO_(2) Reduction Reaction

Electrocatalytic CO_(2) reduction reaction(CO_(2) RR) can store and transform the intermittent renewable energy in the form of chemical energy for industrial production of chemicals and fuels,which can dramatically reduce CO_(2) emission and contribute to carbon-neutral cycle. E cient electrocatalytic reduction of chemically inert CO_(2) is challenging from thermodynamic and kinetic points of view. Therefore,low-cost,highly e cient,and readily available electrocatalysts have been the focus for promoting the conversion of CO_(2). Very recently,interface engineering has been considered as a highly e ective strategy to modulate the electrocatalytic performance through electronic and/or structural modulation,regulations of electron/proton/mass/intermediates,and the control of local reactant concentration,thereby achieving desirable reaction pathway,inhibiting competing hydrogen generation,breaking binding-energy scaling relations of intermediates,and promoting CO_(2) mass transfer. In this review,we aim to provide a comprehensive overview of current developments in interface engineering for CO_(2) RR from both a theoretical and experimental stand-point,involving interfaces between metal and metal,metal and metal oxide,metal and nonmetal,metal oxide and metal oxide,organic molecules and inorganic materials,electrode and electrolyte,molecular catalysts and electrode,etc. Finally,the opportunities and challenges of interface engineering for CO_(2) RR are proposed.

Insight into the Effect of Metal Cations in the Electrolyte on Performance for Electrocatalytic CO_(2)Reduction Reaction

This highlight indicates that the local electrostatic interactions between metal cations and key intermediates facilitate the electrocatalytic CO_(2) reduction reaction.Electrocatalytic CO_(2) reduction reaction(CO_(2)RR)has been considered as a promising strategy to achieve a carbon-neutral cycle and produce valuable fuels and feedstocks.

Cu-Based Materials for Enhanced C_(2+) Product Selectivity in Photo-/Electro-Catalytic CO_(2) Reduction: Challenges and Prospects

Carbon dioxide conversion into valuable products using photocatalysis and electrocatalysis is an effective approach to mitigate global environmental issues and the energy shortages. Among the materials utilized for catalytic reduction of CO_(2), Cu-based materials are highly advantageous owing to their widespread availability, cost-effectiveness, and environmental sustainability. Furthermore, Cu-based materials demonstrate interesting abilities in the adsorption and activation of carbon dioxide, allowing the formation of C_(2+) compounds through C–C coupling process. Herein, the basic principles of photocatalytic CO_(2) reduction reactions(PCO_(2)RR) and electrocatalytic CO_(2) reduction reaction(ECO_(2)RR) and the pathways for the generation C_(2+) products are introduced. This review categorizes Cu-based materials into different groups including Cu metal, Cu oxides, Cu alloys, and Cu SACs, Cu heterojunctions based on their catalytic applications. The relationship between the Cu surfaces and their efficiency in both PCO_(2)RR and ECO_(2)RR is emphasized. Through a review of recent studies on PCO_(2)RR and ECO_(2)RR using Cu-based catalysts, the focus is on understanding the underlying reasons for the enhanced selectivity toward C_(2+) products. Finally, the opportunities and challenges associated with Cu-based materials in the CO_(2) catalytic reduction applications are presented, along with research directions that can guide for the design of highly active and selective Cu-based materials for CO_(2) reduction processes in the future.

Bimetallic In_(2)O_(3)/Bi_(2)O_(3) Catalysts Enable Highly Selective CO_(2) Electroreduction to Formate within Ultra-Broad Potential Windows

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.

Nitrogen-doping boosts ^(*)CO utilization and H_(2)O activation on copper for improving CO_(2) reduction to C_(2+) products

To improve the electrocatalytic transformation of carbon dioxide (CO_(2)) to multi-carbon (C_(2+)) products is of great importance.Here we developed a nitrogen-doped Cu catalyst,by which the maximum C_(2+) Faradaic efficiency can reach 72.7%in flow-cell system,with the partial current density reaching 0.62 A cm^(-2).The in situ Raman spectra demonstrate that the *CO adsorption can be strengthened on such a N-doped Cu catalyst,thus promoting the *CO utilization in the subsequent C–C coupling step.Simultaneously,the water activation can be well enhanced by N doping on Cu catalyst.Owing to the synergistic effects,the selectivity and activity for C_(2+) products over the N-deoped Cu catalyst are much improved.

Electrolyte manipulation on Cu-based electrocatalysts for electrochemical CO_(2) reduction

Electrocatalytic reduction of CO_(2)is crucial for environmental sustainability and renewable energy storage,with Cu-based catalysts excelling in producing high-value C_(2+)products.However,a comprehensive analysis of how specific electrolyte influences Cu-based catalysts is lacking.This review addresses this gap by focusing on how electrolytes impact surface reconstruction and the CO_(2) reduction process on Cu-based electrocatalysts,identifying specific electrolyte compositions that enhance the density and stability of active sites,and providing insights into how different electrolyte environments modulate the selectivity and efficiency of C_(2+)product formation.The review begins by exploring how electrolytes induce favorable surface reconstruction in Cu-based catalysts,affecting surface roughness through dissolution-redeposition of Cu species and interactions with halogens and molecular additives.It also covers changes in crystalline facets of Cu and Cu_(2)O,and oxidation states,highlighting transitions from Cu^(0) to Cu^(δ+)and the stabilization of Cu^(+).The role of electrolytes in the C–C coupling process is examined,emphasizing their effects in modulating mass and charge transfer,CO_(2) adsorption,intermediate evolution,and product desorption.Subsequently,the mechanisms by non-aqueous electrolytes,including organic solvents,ionic liquids,and mixed electrolytes,affecting CO_(2) reduction are analyzed,highlighting the unique advantages and challenges of each type.The review concludes by addressing current challenges,proposing solutions,and research directions,such as optimizing electrolyte composition by integrating diverse cations and anions and employing advanced in-situ characterization techniques.These insights can significantly enhance CO_(2)reduction performance on Cu-based electrocatalysts,advancing efficient and sustainable green energy technologies.

Cobalt phthalocyanine promoted copper catalysts toward enhanced electro reduction of CO_(2)to C_(2):Synergistic catalysis or tandem catalysis?

The activity and selectivity of electrocatalytic CO_(2)reduction reaction(CO_(2)RR)to C_(2)products on metal catalysts can be regulated by molecular surfactants.However,the mechanism behind it remains elusive and debatable.Herein,copper nanowires(Cu NWs)were fabricated and decorated with cobalt phthalocyanine(CoPc).The electronic interaction between the Cu NWs,CoPc,CO_(2) and CO_(2)RR intermediates were explored by density functional theory(DFT)calculations.It was found that the selectivity and activity of CO_(2)RR towards C_(2)products on Cu NWs were considerably enhanced from 35.2%to 69.9%by surface decoration of CoPc.DFT calculations revealed that CO_(2)RR can proceed in the interphase between Cu substrate and CoPc,and the CO_(2)RR intermediates could synergistically bond with both Cu and Co metal centre in CuNWs-CoPc,which favours the adsorption of CO_(2),CO and CO_(2)RR intermediates,thus reducing the free energy for CO-COcoupling towards C_(2)products.The synergistic interaction was further extended to phthalocyanine(Pc)and other metal phthalocyanine derivatives(MPc),where a relatively weaker synergistic interaction of COintermediates with MPc and Cu substrate and only a slight enhancement of CO_(2)RR towards C_(2) products were observed.This study demonstrates a synergistic catalysis pathway for CO_(2)RR,a novel perspective in interpreting the role of CoPc in enhancing the activity and selectivity of CO_(2)RR on Cu NWs,in contrast to the conventional tandem catalysis mechanism.

MOF‐derived 1D/3D N‐doped porous carbon for spatially confined electrochemical CO_(2) reduction to adjustable syngas

Electrochemical reduction of CO_(2) to syngas(CO and H_(2))offers an efficient way to mitigate carbon emissions and store intermittent renewable energy in chemicals.Herein,the hierarchical one‐dimensional/three‐dimensional nitrogen‐doped porous carbon(1D/3D NPC)is prepared by carbonizing the composite of Zn‐MOF‐74 crystals in situ grown on a commercial melamine sponge(MS),for electrochemical CO_(2) reduction reaction(CO_(2)RR).The 1D/3D NPC exhibits a high CO/H_(2) ratio(5.06)and CO yield(31 mmol g^(−1)h^(−1))at−0.55 V,which are 13.7 times and 21.4 times those of 1D porous carbon(derived from Zn‐MOF‐74)and N‐doped carbon(carbonized by MS),respectively.This is attributed to the unique spatial environment of 1D/3D NPC,which increases the adsorption capacity of CO_(2) and promotes electron transfer from the 3D N‐doped carbon framework to 1D carbon,improving the reaction kinetics of CO_(2)RR.Experimental results and charge density difference plots indicate that the active site of CO_(2)RR is the positively charged carbon atom adjacent to graphitic N on 1D carbon and the active site of HER is the pyridinic N on 1D carbon.The presence of pyridinic N and pyrrolic N reduces the number of electron transfer,decreasing the reaction kinetics and the activity of CO_(2)RR.The CO/H_(2) ratio is related to the distribution of N species and the specific surface area,which are determined by the degree of spatial confinement effect.The CO/H_(2) ratios can be regulated by adjusting the carbonization temperature to adjust the degree of spatial confinement effect.Given the low cost of feedstock and easy strategy,1D/3D NPC catalysts have great potential for industrial application.

Chalcogen heteroatoms doped nickel-nitrogen-carbon single-atom catalysts with asymmetric coordination for efficient electrochemical CO_(2) reduction

The electronic configuration of central metal atoms in single-atom catalysts(SACs)is pivotal in electrochemical CO_(2) reduction reaction(eCO_(2)RR).Herein,chalcogen heteroatoms(e.g.,S,Se,and Te)were incorporated into the symmetric nickel-nitrogen-carbon(Ni-N_(4)-C)configuration to obtain Ni-X-N_(3)-C(X:S,Se,and Te)SACs with asymmetric coordination presented for central Ni atoms.Among these obtained Ni-X-N_(3)-C(X:S,Se,and Te)SACs,Ni-Se-N_(3)-C exhibited superior eCO_(2)RR activity,with CO selectivity reaching~98% at-0.70 V versus reversible hydrogen electrode(RHE).The Zn-CO_(2) battery integrated with Ni-Se-N_(3)-C as cathode and Zn foil as anode achieved a peak power density of 1.82 mW cm^(-2) and maintained remarkable rechargeable stability over 20 h.In-situ spectral investigations and theoretical calculations demonstrated that the chalcogen heteroatoms doped into the Ni-N_(4)-C configuration would break coordination symmetry and trigger charge redistribution,and then regulate the intermediate behaviors and thermodynamic reaction pathways for eCO_(2)RR.Especially,for Ni-Se-N_(3)-C,the introduced Se atoms could significantly raise the d-band center of central Ni atoms and thus remarkably lower the energy barrier for the rate-determining step of ^(*)COOH formation,contributing to the promising eCO_(2)RR performance for high selectivity CO production by competing with hydrogen evolution reaction.

CO_(2) reduction reaction pathways on single‐atom Co sites:Impacts of local coordination environment

Single‐atom catalysts have been proposed as promising electrocatalysts for CO_(2) reduction reactions(CO_(2)RR).Co‐N_(4) active sites have attracted wide attention owing to their excellent CO selectivity and activity.However,the effect of the local coordination environment of Co sites on CO_(2) reduction reaction pathways is still unclear.In this study,we investigated the CO_(2) reduction reaction pathways on Co‐N_(4) sites supported on conjugated N_(4)‐macrocyclic ligands with 1,10‐phenanthroline subunits(Co‐N_(4)‐CPY)by density functional theory calculations.The local coordination environment of single‐atom Co sites with N substituted by O(Co‐N_(3)O‐CPY)and C(Co‐N_(3)C‐CPY)was studied for comparison.The calculation results revealed that both C and O coordination break the symmetry of the primary CoN_(4) ligand field and induce charge redistribution of the Co atom.For Co‐N_(4)‐CPY,CO was confirmed to be the main product of CO_(2)RR.HCOOH is the primary product of Co‐N_(3)O‐CPY because of the greatly increased energy barrier of CO_(2) to*COOH.Although the energy barrier of CO_(2) to*COOH is reduced on Co‐N_(3)C‐CPY,the desorption process of*CO becomes more difficult.CH3OH(or CH_(4))are obtained by further*CO hydrogenation reduction when using Co‐N_(3)C‐CPY.This work provides new insight into the effect of the local coordination environment of single‐atom sites on CO_(2) reduction reaction pathways.

Ultralow Ag-assisted carbon-carbon coupling mechanism on Cu-based catalysts for electrocatalytic CO_(2) reduction

Electrocatalytic CO_(2) reduction to C2H4supplies an economically viable route for CO_(2) fixation with the integration of intermittent renewable energy.Cu-based catalysts are capable of catalyzing CO_(2) to C_(2)H_(4),while suffering from the high overpotential and low Faradaic efficiency.In this joint experimentalcomputational work,an Ag-assisted carbon-carbon coupling is exploited on Cu-based catalysts.A systematic characterization analysis suggests that an ultralow quantity of Ag atoms in the Cu catalysts motivates electron transfer from Cu to Ag,regulating the electronic state of highly dispersed Ag.Meanwhile,the Ag incorporation provokes the formation of more oxygen defects on the catalyst surface,improving the adsorption and activation of CO_(2) molecules.Density functional theory studies prove the improvement effect of Ag for CO_(2)to COOH^(*).^(*)CO hydrogenation is energetically more favorable than^(*)CO dimerization pathway,and two^(*)CHO dimerization produces^(*)OCHCHO^(*) key intermediates,which greatly reduces the energy barrier for C_(2)H_(4) formation.

Photo-and Electrocatalytic CO_(2)Reduction Based on Stable Lead-Free Perovskite Cs2PdBr6

All-inorganic lead-free palladium(Pd)halogen perovskites with prominent optoelectronic properties provide admirable potential for selective photo-and electroreduction of CO_(2).But it remains unachieved for effectively converting the CO_(2)to CO with high selectivity on Pd-based perovskites driven by solar light or electricity.Herein,high-quality Cs_(2)PdBr_(6)microcrystals and nanocrystals were synthesized through a facile antisolvent method.Among all the reported pure-phase perovskites,the Cs_(2)PdBr_(6)nanocrystals synthesized at 50℃performed the highest effectiveness on CO_(2)to CO conversion generating 73.8μmol g^(-1)of CO yield with 100%selectivity under visible light illumination(λ>420 nm)for 3 h.Meanwhile,for the first time,we report a new application of lead-free perovskites,in which they are applied to electrocatalysis of CO_(2)reduction reaction.Noticeably,they showed significant electrocatalytic activity(Faradaic yield:78%for CO)and operation stability(10 h).And the surface reaction intermediates were dynamically monitored and precisely unraveled according to the in situ diffuse reflectance infrared Fourier transform spectra investigation.In combination with the density functional theory calculation,the reaction mechanism and pathways were revealed.This work not only provides significant strategies to enhance the photocatalytic performance of perovskites,but also shows excellent potential for their application in electrocatalysis.

Activation of Transition Metal(Fe,Co and Ni)-Oxide Nanoclusters by Nitrogen Defects in Carbon Nanotube for Selective CO_(2) Reduction Reaction

The electrochemical carbon dioxide reduction reaction(CO_(2)RR),which can produce value-added chemical feedstocks,is a proton-coupled-electron process with sluggish kinetics.Thus,highly efficient,cheap catalysts are urgently required.Transition metal oxides such as CoO_(x),FeO_(x),and NiO_(x)are low-cost,low toxicity,and abundant materials for a wide range of electrochemical reactions,but are almost inert for CO_(2)RR.Here,we report for the first time that nitrogen doped carbon nanotubes(N-CNT)have a surprising activation effect on the activity and selectivity of transition metal-oxide(MO_(x)where M=Fe,Ni,and Co)nanoclusters for CO_(2)RR.MO_(x)supported on N-CNT,MO_(x)/N-CNT,achieves a CO yield of 2.6–2.8 mmol cm−2 min−1 at an overpotential of−0.55 V,which is two orders of magnitude higher than MO_(x)supported on acid treated CNTs(MO_(x)/O-CNT)and four times higher than pristine N-CNT.The faraday efficiency for electrochemical CO_(2)-to-CO conversion is as high as 90.3%at overpotential of 0.44 V.Both in-situ XAS measurements and DFT calculations disclose that MO_(x)nanoclusters can be hydrated in CO_(2)saturated KHCO_(3),and the N defects of N-CNT effectively stabilize these metal hydroxyl species under carbon dioxide reduction reaction conditions,which can split the water molecules and provide local protons to inhibit the poisoning of active sites under carbon dioxide reduction reaction conditions.

Surface ligand engineering on metal nanocatalysts for electrocatalytic CO_(2) reduction

Electrocatalytic reduction of CO_(2) into fuels and commodity chemicals has emerged as a potential way to balance the carbon cycle and produce reusable carbon fuels.However,the challenges of the competing reaction of hydrogen evolution reaction,low CO_(2) concentration on the catalyst surface and the diversity of products significantly limit the catalytic activity and selectivity.Hereby,metal nanomaterials,protected by surface sta-bilizing ligands,have been widely studied in the field of CO_(2) reduction due to their structural diversity and outstanding physical and chemical properties.Nevertheless,the surface organic ligands may lower the activity of electrocatalysts,while ligand detachment would cause original structure collapse and selectivity reduction.Therefore,the implementation of strategies based on designing nano-metal catalysts to promote CO_(2) reduction from the perspective of metals and ligands has attracted increasing attention.Herein,we highlight the recent studies on the regulation of surface ligands of metal clusters and metal nanoparticles to promote CO_(2) electro-reduction.Meanwhile,we further summarize the relationship between the surface structure of metal nano-catalysts and the catalytic performance for CO_(2) reduction reaction(CO_(2) RR).This mini review offers an inspiration in remaining challenges and future directions on nano-metal catalysts for electrocatalytic CO_(2) RR.

室温下快速合成Sb-Cu双金属催化剂稳定、高效电催化还原CO_(2)

电化学二氧化碳还原得到合成气(CO/H_(2))和CO是一种利用电能作为原料将CO_(2)转化为有价值产物的潜在方法。报道了一种SbCu双金属催化剂,将第二种金属Sb与Cu合金化来调整Cu对CO的催化活性和选择性,同时通过改变铜源和碳源来调节催化剂的选择性,最终调控产物H_(2)和CO的生成比例。通过改变催化剂的合成条件,生成的合成气比例n(CO)/n(H_(2))可在0.23~6.45之间调控,可以满足费托反应等多种工业反应的供气配比。

从富含缺陷的碳载体到酞菁钴的质子供给用于增强CO_(2)电还原

利用可再生电力将二氧化碳转化为高附加值产品的电催化二氧化碳还原反应(CO_(2)RR)是一项具有革命性潜力的技术,因而备受关注.其中,一氧化碳被视为CO_(2)RR中最具经济效益的产物之一,可直接利用费托合成工艺将其用于合成醛、酮、烃类等产品.酞菁钴(CoPc)作为单位点催化剂,因其高原子利用率和高催化选择性能,在二氧化碳转化为一氧化碳过程中具有很大优势.然而,CoPc无法为CO_(2)RR中的质子化过程提供足够质子,导致其在工业大电流密度下的效率较低.因此,探索一种能够解决CO_(2)RR中质子供给不足问题的高效电催化剂对于提升CO_(2)RR的性能至关重要.本文设计了具有增强质子供给作用的缺陷碳纳米管(d-CNT),将其作为导电载体分散CoPc,用于制备CoPc/d-CNT电催化剂.通过引入富缺陷的碳纳米管(d-CNT),加速水解离进而增加CO_(2)RR的质子供给量.X射线光电子能谱、X射线吸收近边光谱和扩展X射线吸收精细结构谱结果表明,CoPc/d-CNT成功合成,同时保留了CoPc完整的Co-N4配位结构.透射电镜、粉末X射线衍射谱和拉曼光谱共同表明,d-CNT表面缺陷相对于商用CNT明显增加.动力学实验和原位衰减全反射表面增强红外吸收光谱研究表明,含大量缺陷的d-CNT具有加速水解离的能力,显著提高了二氧化碳还原反应过程中的质子供给,从而促进了CoPc_上CO_(2)活化生成*COOH.同时,密度泛函理论计算结果表明,d-CNT表面缺陷位点上从吸附水(*H2O)到质子水(H3O+)的吉布斯自由能为0.74 eV,远低于CNT(超过2 eV),表明d-CNT促进了水解过程和质子传递,再次证实了d-CNT降低了水分子解离的势垒.通过实验和理论的共同验证,阐明了d-CNT中的缺陷能够促进水解离,改善CO_(2)RR反应过程中质子供给,增强CoPc高效催化CO_(2)RR的能力.因此,CoPc/d-CNT混合材料表现出较好的催化性能.在电流密度为500 mA cm^(-2)的流动电池中,CoPc/d-CNT的CO法拉第效率(FECO)高达96%.相对而言,CoPc/CNT在200 mA cm^(-2)时FECO已经下降到90%以下.此外,在150 mA cm^(-2)的电流密度下,CoPc/d-CNT能够在20 h内维持FECO超过90%.综上,本文通过引入具有水解离能力的缺陷碳位点,解决了单位点催化剂CoPc在CO_(2)RR中质子供给不足的问题,为设计高性能催化剂提供了新见解.

理论研究Cu@C_(2)N催化剂表面上水分子对电催化CO_(2)还原反应机理的影响

电催化CO_(2)还原反应(CO_(2)RR)的反应途径涉及多个质子-电子对转移,在水溶剂条件下,质子的来源是水分子,考虑水分子对质子-电子对的转移机制十分必要。本研究提出水辅助氢穿梭模型,与常用的以氢原子作为氢源的直接加氢模型对比,研究水分子在CO_(2)RR中对质子-电子对转移的影响。采用密度泛函理论,系统地研究了铜原子嵌入C_(2)N单层催化剂(Cu@C_(2)N)和石墨烯作为衬底的Cu@C_(2)N/石墨烯复合催化剂(Cu@C_(2)N/G)表面上不同加氢模型的CO_(2)RR反应机理。在水辅助氢穿梭模型中,氢原子与水分子结合形成水合质子,水合质子将自身的氢原子转移到催化剂表面的反应物上形成反应中间体,增强了中间体与催化剂之间的相互作用。此外,在Cu@C_(2)N/G催化剂中,石墨烯将电子转移到表面的Cu@C_(2)N上,提高了催化剂的CO_(2)RR催化活性。进一步,计算了Cu@C_(2)N和Cu@C_(2)N/G催化剂上CO_(2)RR和析氢反应的极限电位,讨论催化剂的活性和选择性。结果表明CO_(2)在低电位下容易生成HCOOH,施加高电位时可以生成CO、CH3OH和CH4并伴随着H2的生成。