Wenyao Chen, Yao Shi, Changwei Liu, Zhouhong Ren, Zikun Huang, Zhou Chen, Xiangxue Zhang, Shanshan Liang, Lei Xie, Cheng Lian, Gang Qian, Jing Zhang, Xi Liu, De Chen, Xinggui Zhou, Weikang Yuan, Xuezhi Duan
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引用次数: 0
摘要
计算得出的火山曲线已成为催化领域的黄金标准,其实际应用通常依赖于相同活性位点假设对成分或尺寸效应的经验解释。在此,我们介绍了一项概念验证研究,该研究揭示了铂钴双金属催化剂的支撑和吸附剂诱导的结构重组,以及不同界面位点之间的相关相互作用,从而提出了取决于协同作用的火山曲线。多重表征、同位素动力学研究和多尺度模拟揭示出,在强 Pt-C 键(金属-支撑界面)和 Co-O 键(金属-吸附剂界面)的驱动下,铂催化剂中 Co 的逐步掺入开始形成富铂合金,并伴有孤立的 Co 物种,然后 Co 分离到外延 CoOx 叠层和相邻的 Co3O4 簇上,最终结构坍塌为无定形合金。因此,在 CO 氧化(气相)、氨硼烷水解(液相)和氢进化反应(电催化)中,确定并量化了三种不同的协同作用,分别涉及铂钴合金/Co3O4 团簇的晶格氧氧化还原、富铂合金/CoOx 叠层的双活性位点工程以及暴露合金内部的电子耦合。与传统的成分/尺寸依赖性曲线相比,协同作用依赖性火山曲线代表了一种进步,是双金属催化理论模型与实验观察之间的桥梁。
Restructuring the interfacial active sites to generalize the volcano curves for platinum-cobalt synergistic catalysis
Computationally derived volcano curve has become the gold standard in catalysis, whose practical application usually relies on empirical interpretations of composition or size effects by the identical active site assumption. Here, we present a proof-of-concept study on disclosing both the support- and adsorbate-induced restructuring of Pt-Co bimetallic catalysts, and the related interplays among different interfacial sites to propose the synergy-dependent volcano curves. Multiple characterizations, isotopic kinetic investigations, and multiscale simulations unravel that the progressive incorporation of Co into Pt catalysts, driven by strong Pt-C bonding (metal-support interfaces) and Co-O bonding (metal-adsorbate interfaces), initiates the formation of Pt-rich alloys accompanied by isolated Co species, then Co segregation to epitaxial CoOx overlayers and adjacent Co3O4 clusters, and ultimately structural collapse into amorphous alloys. Accordingly, three distinct synergies, involving lattice oxygen redox from Pt-Co alloy/Co3O4 clusters, dual-active sites engineering via Pt-rich alloy/CoOx overlayer, and electron coupling within exposed alloy, are identified and quantified for CO oxidation (gas-phase), ammonia borane hydrolysis (liquid-phase), and hydrogen evolution reaction (electrocatalysis), respectively. The resultant synergy-dependent volcano curves represent an advancement over traditional composition-/size-dependent ones, serving as a bridge between theoretical models and experimental observations in bimetallic catalysis.
期刊介绍:
Nature Communications, an open-access journal, publishes high-quality research spanning all areas of the natural sciences. Papers featured in the journal showcase significant advances relevant to specialists in each respective field. With a 2-year impact factor of 16.6 (2022) and a median time of 8 days from submission to the first editorial decision, Nature Communications is committed to rapid dissemination of research findings. As a multidisciplinary journal, it welcomes contributions from biological, health, physical, chemical, Earth, social, mathematical, applied, and engineering sciences, aiming to highlight important breakthroughs within each domain.