Atomic Insight into the Local Structure and Microenvironment of Isolated Co-Motifs in MFI Zeolite Frameworks for Propane Dehydrogenation

被引:121
作者
Hu, Zhong-Pan [1 ]
Qin, Gangqiang [2 ,3 ]
Han, Jingfeng [1 ]
Zhang, Wenna [1 ]
Wang, Nan [1 ,3 ]
Zheng, Yijun [1 ]
Jiang, Qike [2 ]
Ji, Te [4 ]
Yuan, Zhong-Yong [5 ]
Xiao, Jianping [1 ]
Wei, Yingxu [1 ]
Liu, Zhongmin [1 ]
机构
[1] Chinese Acad Sci, IChEM Collaborat Innovat Ctr Chem Energy Mat, Natl Engn Res Ctr Lower Carbon Catalysis Technol, Dalian Natl Lab Clean Energy,Dalian Inst Chem Phy, Dalian 116023, Peoples R China
[2] Chinese Acad Sci, Dalian Inst Chem Phys, State Key Lab Catalysis, Dalian 116023, Peoples R China
[3] Univ Chinese Acad Sci, Beijing 100049, Peoples R China
[4] Chinese Acad Sci, Shanghai Inst Appl Phys, SSRF, Shanghai 201800, Peoples R China
[5] Nankai Univ, Sch Mat Sci & Engn, Minist Educ, Key Lab Adv Energy Mat Chem, Tianjin 300350, Peoples R China
基金
中国博士后科学基金; 中国国家自然科学基金;
关键词
EFFICIENT EPOXIDATION; METHANE HYDROXYLATION; LIGHT ALKANES; SITES; CATALYSTS; ACID; OXIDATION; BETA; NANOPARTICLES; HYDROCARBONS;
D O I
10.1021/jacs.2c02636
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
Embedding metal species into zeolite frameworks can create framework-bond metal sites in a confined microenvironment. The metals sitting in the specific T sites of zeolites and their crystalline surroundings are both committed to the interaction with the reactant, participation in the activation, and transient state achievement during the whole catalytic process. Herein, we construct isolated Co-motifs into purely siliceous MFI zeolite frameworks (Co-MFI) and reveal the location and microenvironment of the isolated Co active center in the MFI zeolite framework particularly beneficial for propane dehydrogenation (PDH). The isolated Co-motif with the distorted tetrahedral stnicture ({( SiO)(2)Co(HO-Si )(2)}, two Co-O-Si bonds, and two pseudo-bridging hydroxyls (Co center dot center dot center dot OH-Si) is located at T-1(7) and T-3(9) sites of the MFI zeolite. DFT calculations and deuterium-labeling reactions verify that the isolated Co-motif together with the MFI microenvironment collectively promotes the PDH reaction by providing an exclusive microenvironment to preactivate C3H8, polarizing the oxygen in Co-O-Si bonds to accept H* ({( SiO)CoH delta- (H delta+O-Si )(3)}), and a scaffold structure to stabilize the C3H7* intermediate. The Co-motif active center in Co-MFI goes through the dynamic evolutions and restoration in electronic states and coordination states in a continuous and repetitive way, which meets the requirements from the series of elementary steps in the PDH catalytic cycle and fulfills the successful catalysis like enzyme catalysis.
引用
收藏
页码:12127 / 12137
页数:11
相关论文
共 56 条
[41]   Function-led design of new porous materials [J].
Slater, Anna G. ;
Cooper, Andrew I. .
SCIENCE, 2015, 348 (6238) :aaa8075
[42]   Cage effects control the mechanism of methane hydroxylation in zeolites [J].
Snyder, Benjamin E. R. ;
Bols, Max L. ;
Rhoda, Hannah M. ;
Plessers, Dieter ;
Schoonheydt, Robert A. ;
Sels, Bert F. ;
Solomon, Edward, I .
SCIENCE, 2021, 373 (6552) :327-+
[43]   The active site of low-temperature methane hydroxylation in iron-containing zeolites [J].
Snyder, Benjamin E. R. ;
Vanelderen, Pieter ;
Bols, Max L. ;
Hallaert, Simon D. ;
Bottger, Lars H. ;
Ungur, Liviu ;
Pierloot, Kristine ;
Schoonheydt, Robert A. ;
Sels, Bert F. ;
Solomon, Edward I. .
NATURE, 2016, 536 (7616) :317-+
[44]   Selective anaerobic oxidation of methane enables direct synthesis of methanol [J].
Sushkevich, Vitaly L. ;
Palagin, Dennis ;
Ranocchiari, Marco ;
van Bokhoven, Jeroen A. .
SCIENCE, 2017, 356 (6337) :523-+
[45]   New Strategies for the Preparation of Sinter-Resistant Metal-Nanoparticle-Based Catalysts [J].
Wang, Lingxiang ;
Wang, Liang ;
Meng, Xiangju ;
Xiao, Feng-Shou .
ADVANCED MATERIALS, 2019, 31 (50)
[46]   Impregnating Subnanometer Metallic Nanocatalysts into Self-Pillared Zeolite Nanosheets [J].
Wang, Ning ;
Sun, Qiming ;
Zhang, Tianjun ;
Mayoral, Alvaro ;
Li, Lin ;
Zhou, Xue ;
Xu, Jun ;
Zhang, Peng ;
Yu, Jihong .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2021, 143 (18) :6905-6914
[47]   Ultrasmall Metal Nanoparticles Confined within Crystalline Nanoporous Materials: A Fascinating Class of Nanocatalysts [J].
Wang, Ning ;
Sun, Qiming ;
Yu, Jihong .
ADVANCED MATERIALS, 2019, 31 (01)
[48]   Spatially isolated cobalt oxide sites derived from MOFs for direct propane dehydrogenation [J].
Wang, Yansu ;
Suo, Yujun ;
Ren, Jin-Tao ;
Wang, Zheng ;
Yuan, Zhong-Yong .
JOURNAL OF COLLOID AND INTERFACE SCIENCE, 2021, 594 :113-121
[49]   Ultrasmall PtZn bimetallic nanoclusters encapsulated in silicalite-1 zeolite with superior performance for propane dehydrogenation [J].
Wang, Yansu ;
Hu, Zhong-Pan ;
Lv, Xianwei ;
Chen, Lei ;
Yuan, Zhong-Yong .
JOURNAL OF CATALYSIS, 2020, 385 :61-69
[50]   Direct Mechanism of the First Carbon-Carbon Bond Formation in the Methanol-to-Hydrocarbons Process [J].
Wu, Xinqiang ;
Xu, Shutao ;
Zhang, Wenna ;
Huang, Jindou ;
Li, Jinzhe ;
Yu, Bowen ;
Wei, Yingxu ;
Liu, Zhongmin .
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2017, 56 (31) :9039-9043