Changfei Jing, Junyang Ding, Peipei Jia, Mengmeng Jin, Lihui Zhou, Xijun Liu, Jun Luo, Sheng Dai
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引用次数: 0
Abstract
The low-energy electrochemical production of hydrogen peroxide (H2O2) has garnered significant attention as a viable alternative to traditional industrial routes, with the goal of achieving carbon neutrality. For their H2O2 selectivity in the two-electron oxygen reduction reaction (ORR), the coordination environment of tungsten (W)-based materials is critical. In this study, atomically dispersed W single atoms were immobilized on N-doped carbon substrates by a facile pyrolysis method to obtain a W single-atom catalyst (W-SAC). The coordination environment of an isolated W single atom with a tetra-coordinated porphyrin-like structure in W-SAC was determined by X-ray photoelectron spectroscopy and X-ray absorption spectroscopy analysis. Notably, the as-prepared W-SAC showed superior two-electron ORR activity in 0.1 M KOH solution, including high onset potential (0.89 V), high H2O2 selectivity (82.5%), and excellent stability. By using differential phase contrast-scanning transmission electron microscopy and density functional theory calculations, it is revealed that the charge symmetry-breaking of W atoms changes the adsorption behavior of the intermediates, leading to enhanced reactivity and selectivity for two-electron ORR. This work broadens the avenue for understanding the charge transfer of W-based electrocatalytic materials and the in-depth reaction mechanism of SACs in two-electron ORR.
过氧化氢(H2O2)的低能耗电化学生产作为传统工业路线的一种可行替代方法,以实现碳中和为目标,引起了广泛关注。在双电子氧还原反应(ORR)中,钨(W)基材料的配位环境对其 H2O2 选择性至关重要。本研究采用简便的热解方法将原子分散的 W 单原子固定在掺杂 N 的碳基底上,从而获得了 W 单原子催化剂(W-SAC)。通过 X 射线光电子能谱和 X 射线吸收光谱分析,确定了 W-SAC 中具有四配位卟啉样结构的孤立 W 单原子的配位环境。值得注意的是,制备的 W-SAC 在 0.1 M KOH 溶液中表现出卓越的双电子 ORR 活性,包括高起始电位(0.89 V)、高 H2O2 选择性(82.5%)和优异的稳定性。通过使用差相对比扫描透射电子显微镜和密度泛函理论计算,发现 W 原子的电荷对称性破坏改变了中间产物的吸附行为,从而提高了双电子 ORR 的反应活性和选择性。这项研究拓宽了人们了解 W 基电催化材料电荷转移的途径,以及 SACs 在双电子 ORR 中的深入反应机理。
期刊介绍:
Carbon Energy is an international journal that focuses on cutting-edge energy technology involving carbon utilization and carbon emission control. It provides a platform for researchers to communicate their findings and critical opinions and aims to bring together the communities of advanced material and energy. The journal covers a broad range of energy technologies, including energy storage, photocatalysis, electrocatalysis, photoelectrocatalysis, and thermocatalysis. It covers all forms of energy, from conventional electric and thermal energy to those that catalyze chemical and biological transformations. Additionally, Carbon Energy promotes new technologies for controlling carbon emissions and the green production of carbon materials. The journal welcomes innovative interdisciplinary research with wide impact. It is indexed in various databases, including Advanced Technologies & Aerospace Collection/Database, Biological Science Collection/Database, CAS, DOAJ, Environmental Science Collection/Database, Web of Science and Technology Collection.