Sicong Qiao, Guikai Zhang, Dong Tian, Wenjie Xu, Wei Jiang, Yuyang Cao, Jun Qian, Jing Zhang, Qun He and Li Song
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引用次数: 0
Abstract
The electrochemical reduction of carbon dioxide (CO2) into formate holds great promise. However, the ongoing competition of parallel reactions, including the generation of hydrogen (H2), carbon monoxide (CO), and multi-carbon products, continues to be a significant factor influencing the formate selectivity. Here, we report a copper-based heterojunction (Cu2O@Cu) precatalyst, which undergoes significant structural reconstruction, resulting in the formation of stepped Cu sites on a hierarchical dendritic array. The formate selectivity of reconstructed Cu2O@Cu can achieve up to 95.9% at a low potential of −0.6 V versus the reversible hydrogen electrode when quaternary ammonium cationic surfactants are introduced. Meticulous in situ spectroscopic and theoretical analyses reveal that the electrically driven alignment of surfactants not only repels hydrated ions, thereby inhibiting proton delivery in H2 evolution, but also interacts with stepped Cu sites to deactivate CO and C–C coupling pathways. The electrified modulation of interfacial microenvironment ultimately suppresses the evolution of H2, CO, and multi-carbon products, ensuring the high-selectivity conversion of CO2 to formate. This study highlights the crucial synergistic effect of structural reconstruction and ligand modification in enhancing electrocatalysis.
用电化学方法将二氧化碳(CO2)还原成甲酸盐前景广阔。然而,平行反应的持续竞争,包括氢气(H2)、一氧化碳(CO)和多碳产物的生成,仍然是影响甲酸酯选择性的一个重要因素。在此,我们报告了一种铜基异质结(Cu2O@Cu)前催化剂,它经历了显著的结构重构,从而在分层树枝状阵列上形成了阶梯状的铜位点。当引入季铵阳离子表面活性剂时,重构后的 Cu2O@Cu 在-0.6 V 的低电位下相对于可逆氢电极的甲酸选择性可达 95.9%。细致的原位光谱和理论分析表明,表面活性剂的电驱动排列不仅能排斥水合离子,从而抑制 H2 演化过程中的质子输送,还能与阶梯状的 Cu 位点相互作用,使 CO 和 C-C 耦合途径失活。界面微环境的电动调节最终抑制了 H2、CO 和多碳产物的演化,确保了 CO2 向甲酸盐的高选择性转化。这项研究强调了结构重构和配体修饰在增强电催化方面的重要协同作用。
期刊介绍:
Energy & Environmental Science, a peer-reviewed scientific journal, publishes original research and review articles covering interdisciplinary topics in the (bio)chemical and (bio)physical sciences, as well as chemical engineering disciplines. Published monthly by the Royal Society of Chemistry (RSC), a not-for-profit publisher, Energy & Environmental Science is recognized as a leading journal. It boasts an impressive impact factor of 8.500 as of 2009, ranking 8th among 140 journals in the category "Chemistry, Multidisciplinary," second among 71 journals in "Energy & Fuels," second among 128 journals in "Engineering, Chemical," and first among 181 scientific journals in "Environmental Sciences."
Energy & Environmental Science publishes various types of articles, including Research Papers (original scientific work), Review Articles, Perspectives, and Minireviews (feature review-type articles of broad interest), Communications (original scientific work of an urgent nature), Opinions (personal, often speculative viewpoints or hypotheses on current topics), and Analysis Articles (in-depth examination of energy-related issues).