The electrochemical CO_(2)reduction reaction to produce multi-carbon(C_(2+)) hydrocarbons or oxygenate compounds is a promising route to obtain a renewable fuel of high energy density.However,producing C_(2+)at high c...The electrochemical CO_(2)reduction reaction to produce multi-carbon(C_(2+)) hydrocarbons or oxygenate compounds is a promising route to obtain a renewable fuel of high energy density.However,producing C_(2+)at high current densities is still a challenge.Herein,we develop a Cu-Zn alloy/Cu-Zn aluminate oxide composite electrocatalytic system for enhanced conversion of CO_(2)to C_(2+)products.The Cu-Zn-Al-Layered Double Hydroxide(LDH) is used as a precursor to decompose into uniform Cu-Zn oxide/Cu-Zn aluminate pre-catalyst.Under electrochemical reduction,Cu-Zn oxide generates Cu-Zn alloy while Cu-Zn aluminate oxide remains unchanged.The alloy and oxide are closely stacked and arranged alternately,and the aluminate oxide induces the strong electron interaction of Cu,Zn and Al,creating a large number of highly active reaction interfaces composed of 0 to+3 valence metal sites.With the help of the interface effect,the optimized Cu_(9)Zn_(1)/Cu_(0.8)Zn_(0.2)Al_(2)O_(4)catalyst achieves a Faradaic efficiency of 88.5% for C_(2+)products at a current density of 400 mA cm^(-2)at-1.15 V versus reversible hydrogen electrode.The in-situ Raman and attenuate total reflectance-infrared absorption spectroscopy(ATR-IRAS) spectra show that the aluminate oxide at the interface significantly enhances the adsorption and activation of CO_(2)and the dissociation of H2O and strengthens the adsorption of CO intermediates,and the alloy promotes the C-C coupling to produce C_(2+)products.This work provides an efficient strategy to construct highly active reaction interfaces for industrial-scale electrochemical CO_(2)RR.展开更多
Electrocatalytic reduction of carbon dioxide is one of the most effective strategies to achieve carbon neutrality and energy sustainability.Although high-value multi-carbon products have been widely studied,limited el...Electrocatalytic reduction of carbon dioxide is one of the most effective strategies to achieve carbon neutrality and energy sustainability.Although high-value multi-carbon products have been widely studied,limited electrocatalysts have been reported for the selective conversion of ethane.More importantly,the factors tuning the selectivity between ethane and ethylene have not been clarified.Here,Zn@Cu nanowire arrays(Zn@Cu-NWAs) catalyst is proposed to stimulate the maintenance of efficient CO_(2)-to-C_(2)H_(6) conversion at high current densities.Meanwhile,in order to investigate the factors affecting the interconversion between ethane and ethylene,the counterpart catalyst that facilitates C–C coupling to ethylene was also synthesized.Time-of-flight secondary-ion mass spectroscopy(TOF-SIMS),in-situ Raman spectroscopy,and simulation results show that Zn@Cu-NWAs can provide a localized proton corridor environment for the formation of ethane,accelerating the further proton-coupled CO_(2) reduction reaction(CO_(2)RR)kinetics.Hence,this catalyst delivered an ethane Faraday efficiency of over 65% at-1.14 V vs.RHE with a total current density of 142.3 mA/cm^(2).This work provides a new perspective on regulating the local microenvironment to modify the selectivity of multi-carbon products.展开更多
结合了三维结构和亲锌物种的集流体构筑策略被认为是构建高稳定锌金属负极的有效方法.然而,高昂的成本和复杂的制备工艺阻碍了其实际应用.本文通过在有均匀Cu^(2+)锚定的碳布集流体(ACC-600@Cu^(2+))上沉积锌,合理设计了一种稳定的三维...结合了三维结构和亲锌物种的集流体构筑策略被认为是构建高稳定锌金属负极的有效方法.然而,高昂的成本和复杂的制备工艺阻碍了其实际应用.本文通过在有均匀Cu^(2+)锚定的碳布集流体(ACC-600@Cu^(2+))上沉积锌,合理设计了一种稳定的三维锌金属复合阳极(Zn@ACC-600@Cu^(2+)).在锌成核过程中,Cu^(2+)原位还原为金属Cu,然后随着锌的进一步沉积,碳布表面逐渐形成均匀的亲锌的Cu-Zn合金界面层.密度泛函理论计算和实验观察表明,Cu-Zn合金界面不仅可以作为锌离子的亲锌沉积点,而且可以提高导电率,使电场和锌离子通量均匀化.因此,ACC-600@Cu^(2+)集流体可以实现高的镀锌/剥离可逆性,并在15.8 mV的极化电压下稳定循环410 h以上.作为概念验证,我们组装的Zn@ACC-600@Cu^(2+)‖MnO_(2)全电池具有良好的电池倍率性能,与原始碳布相比,其比容量显著提高至110 mA h g^(-1).本文提出的原位还原策略为三维锌金属复合负极的设计提供了一种简便且低成本的方法,促进了无枝晶和高稳定锌金属电池的发展.展开更多
基金supported by the National Natural Science Foundation of China (NSFC)(22075201)the National Key Research and Development Program of China (2022YFB4101800)。
文摘The electrochemical CO_(2)reduction reaction to produce multi-carbon(C_(2+)) hydrocarbons or oxygenate compounds is a promising route to obtain a renewable fuel of high energy density.However,producing C_(2+)at high current densities is still a challenge.Herein,we develop a Cu-Zn alloy/Cu-Zn aluminate oxide composite electrocatalytic system for enhanced conversion of CO_(2)to C_(2+)products.The Cu-Zn-Al-Layered Double Hydroxide(LDH) is used as a precursor to decompose into uniform Cu-Zn oxide/Cu-Zn aluminate pre-catalyst.Under electrochemical reduction,Cu-Zn oxide generates Cu-Zn alloy while Cu-Zn aluminate oxide remains unchanged.The alloy and oxide are closely stacked and arranged alternately,and the aluminate oxide induces the strong electron interaction of Cu,Zn and Al,creating a large number of highly active reaction interfaces composed of 0 to+3 valence metal sites.With the help of the interface effect,the optimized Cu_(9)Zn_(1)/Cu_(0.8)Zn_(0.2)Al_(2)O_(4)catalyst achieves a Faradaic efficiency of 88.5% for C_(2+)products at a current density of 400 mA cm^(-2)at-1.15 V versus reversible hydrogen electrode.The in-situ Raman and attenuate total reflectance-infrared absorption spectroscopy(ATR-IRAS) spectra show that the aluminate oxide at the interface significantly enhances the adsorption and activation of CO_(2)and the dissociation of H2O and strengthens the adsorption of CO intermediates,and the alloy promotes the C-C coupling to produce C_(2+)products.This work provides an efficient strategy to construct highly active reaction interfaces for industrial-scale electrochemical CO_(2)RR.
基金financially supported by the Outstanding Youth Project of Guangdong Natural Science Foundation (2021B1515020051)the financial support from the Basic and Applied Basic Research Foundation of Guangdong Province (2021B1515120024, 2022A1515011804)。
文摘Electrocatalytic reduction of carbon dioxide is one of the most effective strategies to achieve carbon neutrality and energy sustainability.Although high-value multi-carbon products have been widely studied,limited electrocatalysts have been reported for the selective conversion of ethane.More importantly,the factors tuning the selectivity between ethane and ethylene have not been clarified.Here,Zn@Cu nanowire arrays(Zn@Cu-NWAs) catalyst is proposed to stimulate the maintenance of efficient CO_(2)-to-C_(2)H_(6) conversion at high current densities.Meanwhile,in order to investigate the factors affecting the interconversion between ethane and ethylene,the counterpart catalyst that facilitates C–C coupling to ethylene was also synthesized.Time-of-flight secondary-ion mass spectroscopy(TOF-SIMS),in-situ Raman spectroscopy,and simulation results show that Zn@Cu-NWAs can provide a localized proton corridor environment for the formation of ethane,accelerating the further proton-coupled CO_(2) reduction reaction(CO_(2)RR)kinetics.Hence,this catalyst delivered an ethane Faraday efficiency of over 65% at-1.14 V vs.RHE with a total current density of 142.3 mA/cm^(2).This work provides a new perspective on regulating the local microenvironment to modify the selectivity of multi-carbon products.
基金supported by the National Natural Science Foundation of China(22001236)the Program for Innovative Research Team(in Science and Technology)in Universities of Henan Province(19IRTSTHN022)Zhengzhou University。
文摘结合了三维结构和亲锌物种的集流体构筑策略被认为是构建高稳定锌金属负极的有效方法.然而,高昂的成本和复杂的制备工艺阻碍了其实际应用.本文通过在有均匀Cu^(2+)锚定的碳布集流体(ACC-600@Cu^(2+))上沉积锌,合理设计了一种稳定的三维锌金属复合阳极(Zn@ACC-600@Cu^(2+)).在锌成核过程中,Cu^(2+)原位还原为金属Cu,然后随着锌的进一步沉积,碳布表面逐渐形成均匀的亲锌的Cu-Zn合金界面层.密度泛函理论计算和实验观察表明,Cu-Zn合金界面不仅可以作为锌离子的亲锌沉积点,而且可以提高导电率,使电场和锌离子通量均匀化.因此,ACC-600@Cu^(2+)集流体可以实现高的镀锌/剥离可逆性,并在15.8 mV的极化电压下稳定循环410 h以上.作为概念验证,我们组装的Zn@ACC-600@Cu^(2+)‖MnO_(2)全电池具有良好的电池倍率性能,与原始碳布相比,其比容量显著提高至110 mA h g^(-1).本文提出的原位还原策略为三维锌金属复合负极的设计提供了一种简便且低成本的方法,促进了无枝晶和高稳定锌金属电池的发展.
