镍族金属团簇在催化加氢过程中的应用

引用本文: 韩波, 程寒松. 镍族金属团簇在催化加氢过程中的应用[J]. 物理化学学报, 2017, 33(7): 1310-1323. doi: 10.3866/PKU.WHXB201704172 shu

Citation: HAN Bo, CHENG Han-Song. Nickel Family Metal Clusters for Catalytic Hydrogenation Processes[J]. Acta Physico-Chimica Sinica, 2017, 33(7): 1310-1323. doi: 10.3866/PKU.WHXB201704172 shu

镍族金属团簇在催化加氢过程中的应用

韩波 ,
程寒松

中国地质大学(武汉)材料科学与化学学院, 可持续能源实验室, 武汉 430074
基金项目:
国家自然科学基金（21473164，21203169，21233006），中国地质大学（武汉）中央高校基本科研业务费以及空气与化学品公司资助项目

摘要: 贵金属纳米颗粒具有优异的催化活性，是异相催化反应中的重要角色。作为一种理想的研究模型，气相金属团簇被广泛应用于在原子和分子尺度探究催化反应的机理。在本专论中，我们将本课题组近年来关于氢气在镍族金属团簇上的解离吸附进行了回顾。首先，我们对比了不同金属团簇的结构演化规律和相对稳定性。随后，我们系统研究了H₂分子在金属团簇上的解离吸附行为，揭示了不同金属对H―H键的解离能力。为了表征不同金属团簇的催化活性，我们定义了两个关键参数：氢气的解离吸附能（ΔE_CE）和H原子的连续脱附能（ΔE_DE）。结果显示，随着H覆盖度的增大，ΔE_CE和ΔE_DE都呈现显著的下降。由于在实际的催化反应中，氢气总是维持在一定的分压下，这就意味着催化剂金属应该总是处于较高的H覆盖度下。因此，通过处于H饱和状态下的ΔE_CE和ΔE_DE来评估金属团簇的催化能力是合理可行的。我们发现，在饱和H吸附状态下，每一个Pt原子可以容纳4个H原子，而每一个Pd或Ni原子则只能吸附2个H原子。考虑到H原子在这些团簇上的脱附能力相当，Pt团簇相对较高的H吸附量将极大提高其在加氢过程中的催化活性。最后，我们系统研究了带电状态对Pt团簇催化性能的影响规律。结果显示，在H覆盖度较低时，H₂分子的解离以及H原子的脱附过程受Pt团簇带电状态的影响较大。在饱和H吸附时，由于大量H原子的吸附，电荷的影响被平均化到每个Pt―H键上，导致ΔE_CE和ΔE_DE都收敛到一个非常小的区域。此外，当团簇的尺寸增大时，其所带的电荷被大量的Pt原子分摊，每个Pt原子仅携带极少的电荷，使得电荷的影响已经可以忽略。

关键词:

English

Nickel Family Metal Clusters for Catalytic Hydrogenation Processes

HAN Bo ,
CHENG Han-Song

Sustainable Energy Laboratory, Faculty of Materials Science and Chemistry, China University of Geosciecnes(Wuhan), Wuhan 430074, P. R. China
Received Date: 12 December 2016
Revised Date: 05 April 2017
Available Online: 17 April 2017
Fund Project:
The project was supported by the National Natural Science Foundation of China (21473164, 21203169, 21233006) and the Fundamental Research Funds for the Central Universities, China University of Geosciences, China, and Air Products and Chemicals, Inc.

Abstract: Nanoparticles of precious metals play an important role in many heterogeneous catalytic reactions due to their excellent catalytic performance. As an idealized model, gas phase metal clusters have been extensively utilized to understand catalytic mechanisms at a molecular level. Here we provide an overview of our recent studies on H₂ dissociative chemisorption on nickel family clusters. The structure evolution and the stability of the metal clusters were first compared. H₂ dissociation on the clusters was then carefully addressed to understand the capability of metal clusters to break the H-H bond. Two key parameters, the dissociative chemisorption energy (ΔE_CE) and the H sequential desorption energy (ΔE_DE),were employed to characterize the catalytic activity of metal clusters. Our results show that both ΔE_CE and ΔE_DE decline significantly as the H coverage increases. Since the catalyst is in general covered entirely by H atoms and H₂ molecules in a typical hydrogenation process, and maintained at a pre-determined pressure of H₂ gas, we can rationally use the calculated ΔE_CE and ΔE_DE values at full H saturation to address the activity of metal clusters. Our results suggest that at full H coverage, each Pt atom is essentially capable of adsorbing 4 H atoms, while each Ni or Pd atom can only accommodate 2 H atoms. Considering the similar values of H desorption energies on Pt and Pd clusters, the higher average H capacity per Pt atom could probably lead to a faster reaction rate because more active H atoms are produced on the Pt catalyst particles in the hydrogenation process. Finally, the charge sensitivity of the key catalytic properties of Pt clusters for hydrogenation was systematically evaluated. The results show that the dissociation of H₂ and H desorption are strongly correlated to the charge state of the Pt clusters at low H coverage. However, at high H-capacities, both ΔE_CE and ΔE_DE fall into a narrow range, suggesting that the charge can be readily dispersed and that the Pt-H bonds average the interaction between clusters and H atoms. As a result, the H-capacities on charged clusters were found to be similar as the cluster size increased; in case of sufficiently large clusters, the reactivity of a fully saturated cluster was no longer sensitive to its charge state.

Key words:

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沈阳化工大学材料科学与工程学院沈阳 110142

镍族金属团簇在催化加氢过程中的应用

English

Nickel Family Metal Clusters for Catalytic Hydrogenation Processes

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CCS Chemistry：颜徐州、鲍哲南：你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

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CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

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通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

镍族金属团簇在催化加氢过程中的应用

English

Nickel Family Metal Clusters for Catalytic Hydrogenation Processes

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南： 你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

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