Electrocatalytic CO(2) Reduction on CuO(x) Nanocubes: Tracking the Evolution of Chemical State, Geometric Structure, and Catalytic Selectivity using Operando Spectroscopy.
Electrocatalytic CO(2) Reduction on CuO(x) Nanocubes: Tracking the Evolution of Chemical State, Geometric Structure, and Catalytic Selectivity using Operando Spectroscopy.
复制标题
电催化CO（2）使用Operando光谱法跟踪化学状态，几何结构和催化选择性的演变的CuO（X）纳米管的降低。
DOI：
10.1002/anie.202007136
复制
发表时间：
2020-10-05
期刊：
影响因子：
--
通讯作者：
Strasser P
中科院分区：
文献类型：
--
作者：
Möller T;Scholten F;Thanh TN;Sinev I;Timoshenko J;Wang X;Jovanov Z;Gliech M;Roldan Cuenya B;Varela AS;Strasser P
将二氧化碳（CO2）直接电化学转化为多碳（C2+）产物仍然面临着基础和技术挑战。虽然小面控制和氧化物衍生的Cu材料被吹捧为有前途的催化剂，但它们的稳定性仍然存在问题，而且人们对其了解甚少。在本文中，我们揭示了在低电流H电池和高电流气体扩散电极（GDE）中使用中性pH缓冲液条件操作期间，支撑和未支撑的Cu 2 O纳米立方体的化学和形态状态的变化。虽然未负载的纳米立方体实现了持续40小时约60%的C2+法拉第效率，但碳载体上的分散体使选择性模式急剧向C1产物转变。 Operando XAS和时间分辨电子显微镜显示了立方体形状的降解，并且在碳载体的存在下，在本体Cu 2 O的惊人缓慢还原期间形成小的Cu晶种。最初富含（100）的小面结构可能对催化选择性没有控制作用，而氧化物衍生的欠配位晶格缺陷的产生可以支持高C2+产物产率。纳米尺寸的Cu 2 O立方体可以追踪控制CO2还原反应（CO2 RR）选择性的化学和结构因素。法拉第产物效率随时间的变化可以与表面和本体的化学状态以及负载和非负载纳米立方体（S-NC，U-NC）的催化剂形态的变化有关。
The direct electrochemical conversion of carbon dioxide (CO2) into multi‐carbon (C2+) products still faces fundamental and technological challenges. While facet‐controlled and oxide‐derived Cu materials have been touted as promising catalysts, their stability has remained problematic and poorly understood. Herein we uncover changes in the chemical and morphological state of supported and unsupported Cu2O nanocubes during operation in low‐current H‐Cells and in high‐current gas diffusion electrodes (GDEs) using neutral pH buffer conditions. While unsupported nanocubes achieved a sustained C2+ Faradaic efficiency of around 60 % for 40 h, the dispersion on a carbon support sharply shifted the selectivity pattern towards C1 products. Operando XAS and time‐resolved electron microscopy revealed the degradation of the cubic shape and, in the presence of a carbon support, the formation of small Cu‐seeds during the surprisingly slow reduction of bulk Cu2O. The initially (100)‐rich facet structure has presumably no controlling role on the catalytic selectivity, whereas the oxide‐derived generation of under‐coordinated lattice defects, can support the high C2+ product yields. Cu2O cubes of nanometer‐sized dimensions allow the chemical and structural factors that control the selectivity of the CO2 reduction reaction (CO2RR) to be traced. The Faradaic product efficiencies over time can be linked to changes in the chemical state at the surface and bulk and in the catalyst morphology for supported and unsupported nanocubes (S‐NC, U‐NC).
登录
查看更多内容
影响因子：
16.6
作者：
Huang J;Hörmann N;Oveisi E;Loiudice A;De Gregorio GL;Andreussi O;Marzari N;Buonsanti R
通讯作者：
Buonsanti R
影响因子：
5.7
作者：
Eilert, Andre;Roberts, F. Sloan;Nilsson, Anders
通讯作者：
Nilsson, Anders
影响因子：
3.7
作者：
Jovanov, Zarko P.;de Araujo, Jorge Ferreira;Strasser, Peter
通讯作者：
Strasser, Peter
影响因子：
29.4
作者：
Chen, Ye;Fan, Zhanxi;Zhang, Hua
通讯作者：
Zhang, Hua
DOI：
10.1073/pnas.1701405114
发表时间：
2017-06-27
影响因子：
11.1
作者：
Favaro, Marco;Xiao, Hai;Crumlin, Ethan J.
通讯作者：
Crumlin, Ethan J.