Single Pd atom and Pd dimer embedded graphene catalyzed formic acid dehydrogenation: A first-principles study
Single Pd atom and Pd dimer embedded graphene catalyzed formic acid dehydrogenation: A first-principles study
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单 Pd 原子和 Pd 二聚体嵌入石墨烯催化甲酸脱氢：第一性原理研究
DOI：
10.1016/j.ijhydene.2018.02.129
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发表时间：
2018-04-05
影响因子：
7.2
通讯作者：
Yang, Jinlong
中科院分区：
文献类型：
--
作者：
Luo, Qiquan;Zhang, Wenhua;Yang, Jinlong
采用密度泛函理论计算研究了甲酸在一系列候选催化剂上的催化分解反应。候选催化剂通过嵌入石墨烯中的单空位和双空位中的单个Pd原子（Pd-1 m-G vs. Pd-1d-G）以及嵌入石墨烯中的二空位、三空位和四空位中的Pd二聚体（Pd-2d-G vs. Pd-2 t-G vs. Pd-2 q-G）来建模。这些催化剂可以有效地和选择性地催化甲酸脱氢成氢气。Pd-2d-G是五种模型中最有利的催化剂，其速率决定步骤势垒仅为0.68 eV，这与最活跃的催化剂之一，即，Pd（111）。Pd-1d-G的活性相对较低，其速率决定阶跃能垒为0.90 eV。其余三种模型，即，Pd-1 m-G、Pd-2 t-G和Pd-2 q-G的势垒分别为1.26、1.12和1.06 eV。在这项工作中研究的模型催化剂是有前途的减少使用的贵金属和稀有金属钯相比，钯本体催化剂。此外，与Pd纳米颗粒催化剂不同，本工作中的模型催化剂阐明了催化机理。(C)2018年氢能出版有限责任公司。由爱思唯尔有限公司出版。保留所有权利。
The catalytic decomposition of formic acid was studied on a series of candidate catalysts using density functional theory calculations. The candidate catalysts were modelled by a single Pd atom embedded in mono- and divacancy in graphene (Pd-1m-G vs. Pd-1d-G), as well as a Pd dimer embedded in di-, tri-, and quadrivacancy in graphene (Pd-2d-G vs. Pd-2t-G vs. Pd-2q-G). These catalysts can effectively and selectively catalyze formic acid dehydrogenation into hydrogen. Pd-2d-G is the most favorable catalyst among the five models with the rate-determining step energy barrier of only 0.68 eV, which is comparable to one of the most active catalysts i.e., Pd(111). Pd-1d-G is comparatively less active, with the rate-determining step energy barrier of 0.90 eV. The rest of the three models, i.e., Pd-1m-G, Pd-2t-G and Pd-2q-G, have energy barriers of 1.26, 1.12 and 1.06 eV, respectively. The model catalysts studied in this work are promising for reducing usage of the precious and rare metal Pd compared with Pd bulk catalysts. Additionally, unlike Pd nanoparticle catalysts, the model catalysts in this work clarify the catalytic mechanism. (C) 2018 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.