The Role of Electronic Structure in the Hydrogen Evolution Reaction Dynamics as Catalyzed by Ru-based Complexes

IF 2.9 3区化学 Q3 CHEMISTRY, PHYSICAL

Physical Chemistry Chemical Physics Pub Date : 2025-09-23 DOI:10.1039/d5cp03035h

Andrea Severini, Camilla Ferrari, Marianna Burello, Francesco Vizza, Marco Bonechi, Riccardo Chelli, Massimo Innocenti, Fabrizio Roncaglia, Claudio Fontanesi

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Abstract

The catalytic activity for the hydrogen evolution reaction of three structurally related ruthenium catalysts is compared: a di-nuclear [Ru 2 (OTf)(m-H)(Me 2 dad)(dbcot) 2 ] (C1) and two mononuclear analogues (C2, C3). The reaction mechanism is analyzed at a molecular level by using ab-initio DFT calculation to determine singular-points on the potential energy surface (PES). Then, time dependent behavior is investigated by calculationing molecular dynamic (MD) trajectories, within the Dynamic Reaction Coordinate (DRC) paradigm. Displacement of molecular hydrogen results the ratedetermining step. C2 shows a promising low activation barrier: 8.6 kcal/mol, although H 2 release is kinetically slower. C3 yields molecular hydrogen but fails its release, even when provided with kinetic energy larger than the activation barrier (24.4 kcal/mol), revealing unforeseen mechanistic traps, beyond purely energetic considerations. This work underscores how ligand coordination flexibility critically affects the efficiency of hydrogen catalysis, paving the way for the rational design of novel catalysts.

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电子结构在钌基配合物催化析氢反应动力学中的作用

比较了三种结构相关的钌催化剂：双核[Ru 2 (OTf)(m-H)(Me 2 dad)(dbcot) 2] （C1）和两种单核类似物（C2, C3）对析氢反应的催化活性。利用ab-initio DFT计算确定势能面上的奇异点，在分子水平上分析了反应机理。然后，在动态反应坐标（DRC）范式下，通过计算分子动力学（MD）轨迹来研究时间依赖性行为。氢分子的位移产生速率决定步骤。C2的活化势垒较低，为8.6 kcal/mol，但h2的释放速度较慢。C3产生氢分子，但不能释放氢分子，即使提供的动能大于激活势垒（24.4千卡/摩尔），揭示了不可预见的机械陷阱，超出了纯粹的能量考虑。这项工作强调了配体配位灵活性对氢催化效率的重要影响，为合理设计新型催化剂铺平了道路。

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来源期刊

Physical Chemistry Chemical Physics 化学-物理：原子、分子和化学物理

CiteScore

5.50

自引率

9.10%

发文量

2675

审稿时长

2.0 months

期刊介绍： Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.