A dendritic Cu/Cu_(2)O structure with high curvature enables rapid and efficient reduction of carbon dioxide to C_(2) in an H-cell

Electrocatalytic reduction of CO_(2)(CO_(2)RR)to multicarbon products is an efficient approach for ad-dressing the energy crisis and achieving carbon neutrality.In H-cells,achieving high-current C_(2)products is challenging because of the inefficient mass transfer of the catalyst and the presence of the hydrogen evolution reaction(HER).In this study,dendritic Cu/Cu_(2)O with abundant Cu^(0)/Cu^(+)interfaces and numerous dendritic curves was synthesized in a CO_(2)atmosphere,resulting in the high selectivity and current density of the C_(2)products.Dendritic Cu/Cu_(2)O achieved a C_(2)Faradaic efficiency of 69.8%and a C_(2)partial current density of 129.5 mA cm^(-2)in an H-cell.Finite element simulations showed that a dendritic structure with a high curvature generates a strong electric field,leading to a localized CO_(2)concentration.Additionally,DRT analysis showed that a dendritic struc-ture with a high curvature actively adsorbed the surrounding high concentration of CO_(2),enhancing the mass transfer rate and achieving a high current density.During the experiment,the impact of the electronic structure on the performance of the catalyst was investigated by varying the atomic ratio of Cu^(0)/Cu^(+) on the catalyst surface,which resulted in improved ethylene selectivity.Under the optimal atomic ratio of Cu^(0)/Cu^(+),the charge transfer resistance was minimized,and the desorption rate of the intermediates was low,favoring C_(2) generation.Density functional theory calculations indicated that the Cu^(0)/Cu^(+) interfaces exhibited a lower Gibbs free energy for the rate-determining step,enhancing C_(2)H_(4) formation.The Cu/Cu_(2)O catalyst also exhibited a low Cu d-band center,which enhanced the adsorption stability of *CO on the surface and facilitated C_(2)formation.This observa-tion explained the higher yield of C_(2) products at the Cu^(0)/Cu^(+) interface than that of H_(2) under rapid mass transfer.The results of the net present value model showed that the H-cell holds promising industrial prospects,contingent upon it being a catalyst with both high selectivity and high current density.This approach of integrating the structure and composition provides new insights for ad-vancing the CO_(2)RR towards high-current C_(2) products.

B原子掺杂调控CuIn纳米合金电子结构以实现电化学CO_(2)还原宽电位活性

杂原子掺杂可以调节电子结构以调整中间体吸附并优化反应路径,是设计高效CO_(2)还原反应(CO_(2)RR)催化剂的有应用前景的方法.B原子是常用的掺杂剂,引入B原子可以有效打破*COOH和OCHO*中间体的吉布斯自由能线性关系,并且可以通过与CO_(2)中O原子结合来增强CO_(2)吸附能力.B掺杂碳材料、单金属和金属氧化物的研究结果表明,B原子掺杂催化剂的CO_(2)RR活性和/或选择性有明显提高,然而多数报道的单个活性位点的B掺杂催化剂仅表现出在相对狭窄的电位范围内的CO_(2)RR高性能,设计制备CO_(2)RR的宽电位高选择性催化剂仍是巨大挑战.研究表明,合金化是提供多种类的活性位点相互协调和增强催化剂固有活性,进而改善CO_(2)RR性能并调节产物分布的可行策略.引入B原子到合金中以调节电子结构,最终优化关键中间体吸附的活性位点,对于寻找具有宽电位窗口的先进催化剂具有重要意义.本文提出了一种通过B掺杂调节CuIn合金电子结构以实现宽电位高选择性的电子工程策略.所制得的B掺杂CuIn合金(CuIn(B))在–0.6 V(vs.RHE)时表现出99%的CO法拉第效率(FECO),并在一个宽的阴极电化学窗口(400 m V)内保持了超过90%的较高FECO.同时,采用X射线光电子能谱(XPS)和CO_(2)吸附实验等手段研究了CuIn(B)性能提升的原因,结果表明,B原子与CuIn之间存在强烈的相互作用,改变了CuIn的电子结构.CO_(2)吸附结果表明,CuIn(B)比CuIn拥有更强的CO_(2)吸附能力,证明它具有潜在的快速CO_(2)RR反应动力学.进一步通过密度泛函理论(DFT)模拟研究了催化剂的热力学反应能量学以揭示CO_(2)RR机制,结果表明,*COOH更倾向于在CuIn(B)上形成,且*CO与CuIn(B)催化位点的结合强度最佳,更利于CO_(2)还原反应为CO,而CuIn更利于作为HER的活性位点;决速步骤是*CO中间体向CO转移,以实现高CO选择性;热力学限制电位研究表明,CuIn(B)大大提高了CO_(2)到CO转化的选择性.随后通过差分电荷密度研究也进一步证明了电荷转移过程是从CuIn位点到B位点.此外,根据d带理论,催化剂中Cu和In原子的投影态密度和d带中心(Ed)研究进一步证明了催化剂结构中的电子价态的变化,与XPS结果相符;引入B可以优化催化剂的电子结构,从而调节催化剂和中间体之间的结合能力,实现了CO_(2)RR在宽电位范围内的高活性和选择性.综上,本文对于电化学CO_(2)RR机理的基础理解和其实际应用具有促进作用.

Transition metal (Mo, Fe, Co, and Ni)-based catalysts for electrochemical CO_2 reduction

The electrochemical conversion of CO2 into value-added chemicals and fuels has attracted wide-spread concern since it realizes the recycling of greenhouse gases. Production of new materials lies at the very core of this technology as it enables the improvement of developmental efficiency and selectivity by chemical optimization of morphology and electronic structure. Transition metal-based catalysts are particularly appealing as their d bands have valence electrons which are close to the Fermi level and hence overcome the intrinsic activation barriers and reaction kinetics. The study of Mo, Fe, Co, and Ni-based materials in particular is a very recent research subject that offers various possibilities in electrochemical CO2 reduction applications. Herein, we summarize the recent re-search progress of Mo, Fe, Co, and Ni-based catalysts and their catalytic behavior in electrochemical CO〈sub〉2 reduction. We particularly focus on the relationship between structures and properties, with examples of the key features accounting for the high efficiency and selectivity of the CO2 reduction process. The most significant experimental and theoretical improvements are highlighted. Finally, we concisely discuss the scientific challenges and opportunities for transition metal-based catalysts.

Cu/CdcO_(3)catalysts for efficient electrochemical CO_(2)reduction over the wide potential window

High efficiency and low-cost catalyst-driven electrocatalytic CO_(2)reduction to CO production are of great significance for energy storage and development.The severe competitive hydrogen evolution reaction occurs at large negative potential window limits the achievement of the target product from CO_(2)at high efficiency.Here,we successfully prepared Cu_(x)/CdcO_(3)composite catalyst rich in interfaces,in which achieved high CO Faraday eficiency exceeded 90%in a wide potential window of 700 mV and highest value up to 97.9%at-0.90V vs.RHE.The excellent performance can be ascribed to the positive contribution of Cu_(x)/CdcO_(3),which maintains a suitable high local pH value during electrochemical reduction,thus inhibiting the competitive hydrogen evolution reaction.Moreover,the compact structure between Cu and CdCO_(3)ensures fast electron transfer both inside catalysts and interface,thus speeding up the reaction kinetics of CO_(2)to CO conversion.Theoretically calculations further prove that the combination of Cu and CdcO_(3)provides the well-defined electronic structure for intermediates adsorption,significantly reducing the reaction barrier for the formation of co.This work provides new insights into the design of eficient electrochemical CO_(2)reduction catalysts for inhibiting hydrogen evolution by adjusting the local pH effect.