Complementary Operando Spectroscopy identification of in-situ generated metastable charge-asymmetry Cu(2)-CuN(3) clusters for CO(2) reduction to ethanol.
Complementary Operando Spectroscopy identification of in-situ generated metastable charge-asymmetry Cu(2)-CuN(3) clusters for CO(2) reduction to ethanol.
复制标题
DOI：
10.1038/s41467-022-29035-8
复制
发表时间：
2022-03-11
影响因子：
16.6
通讯作者：
Wang Y
中科院分区：
文献类型：
--
作者：
Su X;Jiang Z;Zhou J;Liu H;Zhou D;Shang H;Ni X;Peng Z;Yang F;Chen W;Qi Z;Wang D;Wang Y
铜基材料可以可靠地将二氧化碳转化为多碳产物，但它们的活性和产物选择性差。电催化剂的原子结构-活性关系对选择性的影响一直存在争议，这主要是由于缺乏系统的多维度操作条件研究。在本文中，我们合成了高性能的CO2 RR催化剂，其包含负载在N掺杂的碳纳米片上的CuO簇，其表现出73%的高C2+产物法拉第效率，包括51%的不错的乙醇选择性，在-1.1 V vs. RHE下的部分电流密度为14.4 mA/cm−2。我们证明了催化剂的结构重组，并跟踪了反应条件下活性状态的变化，提出了该催化剂的原子结构与活性的关系。Operando XAS、XANES模拟和准原位XPS分析确定了从分散的CuO团簇到Cu 2-CuN 3团簇的可逆电位依赖性转变，这是最佳的位置。如果没有外加电势，这个团就不可能存在。N掺杂通过调整Cu原子与N掺杂碳界面之间的电荷分布，使还原后的Cu原子团簇均匀分散，保持了良好的稳定性和较高的活性。结合Operando FTIR和DFT计算发现，Cu 2-CuN 3团簇中存在电荷不对称位点，CH 3 * 的吸附强化了这些电荷不对称位点，有利于高效不对称乙醇的形成.铜基材料可以将二氧化碳转化为多碳产物，但活性和选择性差。在这里，作者报道了负载在氮掺杂碳纳米片上的CuO簇用于将CO2还原为乙醇，并研究了在操作过程中催化位点的变化。
Copper-based materials can reliably convert carbon dioxide into multi-carbon products but they suffer from poor activity and product selectivity. The atomic structure-activity relationship of electrocatalysts for the selectivity is controversial due to the lacking of systemic multiple dimensions for operando condition study. Herein, we synthesized high-performance CO2RR catalyst comprising of CuO clusters supported on N-doped carbon nanosheets, which exhibited high C2+ products Faradaic efficiency of 73% including decent ethanol selectivity of 51% with a partial current density of 14.4 mA/cm−2 at −1.1 V vs. RHE. We evidenced catalyst restructuring and tracked the variation of the active states under reaction conditions, presenting the atomic structure-activity relationship of this catalyst. Operando XAS, XANES simulations and Quasi-in-situ XPS analyses identified a reversible potential-dependent transformation from dispersed CuO clusters to Cu2-CuN3 clusters which are the optimal sites. This cluster can’t exist without the applied potential. The N-doping dispersed the reduced Cun clusters uniformly and maintained excellent stability and high activity with adjusting the charge distribution between the Cu atoms and N-doped carbon interface. By combining Operando FTIR and DFT calculations, it was recognized that the Cu2-CuN3 clusters displayed charge-asymmetric sites which were intensified by CH3* adsorbing, beneficial to the formation of the high-efficiency asymmetric ethanol. Copper-based materials can convert carbon dioxide into multi-carbon products but suffer from poor activity and selectivity. Here, the authors report CuO clusters supported on nitrogen-doped carbon nanosheets for the reduction CO2-to-ethanol, and investigate the change in the catalytic sites while in operation.
登录
查看更多内容
影响因子：
5.7
作者：
Eilert, Andre;Roberts, F. Sloan;Nilsson, Anders
通讯作者：
Nilsson, Anders
氟哌啶醇结合的 D-2 多巴胺受体结构激发了亚型选择性配体的发现
影响因子：
16.6
作者：
Fan, Luyu;Tan, Liang;Wang, Sheng
通讯作者：
Wang, Sheng
影响因子：
12.9
作者：
Kruppe, Christopher M.;Krooswyk, Joel D.;Trenary, Michael
通讯作者：
Trenary, Michael
DOI：
10.1073/pnas.1612106114
发表时间：
2017-02-21
影响因子：
11.1
作者：
Cheng, Tao;Xiao, Hai;Goddard, William A., III
通讯作者：
Goddard, William A., III
影响因子：
6.7
作者：
Ghodselahi, T.;Vesaghi, M. A.;Lameii, M.
通讯作者：
Lameii, M.