### 镍族金属团簇在催化加氢过程中的应用

• 收稿日期:2016-12-12 发布日期:2017-05-31
• 通讯作者: 程寒松 E-mail:chghs2@gmail.com
• 作者简介:HAN Bo is an Associate Professor of Chemistry at China University of Geosciences Wuhan. His current research interests focus on computational chemistry and materials, including surface chemistry, energy materials, homogeneous and heterogeneous catalysis|CHENG Han-Song is a Professor of Chemistry at China University of Geosciences Wuhan. In 2009, he was inducted into the "National 1000 Talents Plan" program in China and has served as the director of Sustainable Energy Laboratory at the university since then. His research interest lies in the area of first principles simulations and experimental development of novel materials for gas storage and separation, catalysis, battery electrolytes, and proton exchange membrane fuel cells. He is an author of over 200 peer-reviewed publications and an inventor of over 50 U.S. patents and patent applications
• 基金资助:
国家自然科学基金(21473164);国家自然科学基金(21203169);国家自然科学基金(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

### Nickel Family Metal Clusters for Catalytic Hydrogenation Processes

Bo HAN,Han-Song CHENG*()

• Received:2016-12-12 Published:2017-05-31
• Contact: Han-Song CHENG E-mail:chghs2@gmail.com
• Supported by:
the National Natural Science Foundation of China(21473164);the National Natural Science Foundation of China(21203169);the National Natural Science Foundation of China(21233006);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 (ΔECE) and the H sequential desorption energy (ΔEDE), were employed to characterize the catalytic activity of metal clusters. Our results show that both ΔECE and ΔEDE 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 ΔECE and ΔEDE 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 ΔECE and ΔEDE 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.

MSC2000:

• O641