TiO2负载的高分散Cd团簇催化剂高效催化CO2加氢制甲醇

doi:10.1016/S1872-2067(21)63907-4

催化学报 ›› 2022, Vol. 43 ›› Issue (3): 761-770.DOI: 10.1016/S1872-2067(21)63907-4

TiO₂负载的高分散Cd团簇催化剂高效催化CO₂加氢制甲醇

王集杰^a^,^†, Jittima Meeprasert^b^,^†, 韩哲^a^,^c^,^†, 王欢^a, 冯振东^a^,^d, 汤驰洲^a^,^d, 沙峰^a^,^c, 唐珊^a^,^d, 李冠娜^e^,^f, Evgeny A. Pidko^b^,^#(), 李灿^a^,^*()

^a中国科学院大连化学物理研究所, 催化基础国家重点实验室, 辽宁大连 116023, 中国
^b代尔夫特理工大学化学工程系, 代尔夫特, 荷兰
^c南开大学, 材料科学与工程学院, 天津 300350, 中国
^d中国科学院大学, 北京 100049, 中国
^e瓦格宁根大学生物质化学与技术, 瓦格宁根, 荷兰
^f瓦格宁根大学有机化学实验室, 瓦格宁根, 荷兰

收稿日期:2021-05-27 修回日期:2021-05-27 出版日期:2022-03-18 发布日期:2022-02-18
通讯作者: Evgeny A. Pidko,李灿
作者简介:第一联系人：
^†共同第一作者
基金资助:
国家重点研发计划(2017YFB0702800);人工光合成基础科学中心(FReCAP)(22088102);国家自然科学基金(21802139);中国科学院青年创新促进会(2019183)

Highly dispersed Cd cluster supported on TiO₂ as an efficient catalyst for CO₂ hydrogenation to methanol

Jijie Wang^a^,^†, Jittima Meeprasert^b^,^†, Zhe Han^a^,^c^,^†, Huan Wang^a, Zhendong Feng^a^,^d, Chizhou Tang^a^,^d, Feng Sha^a^,^c, Shan Tang^a^,^d, Guanna Li^e^,^f, Evgeny A. Pidko^b^,^#(), Can Li^a^,^*()

^aState Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, Liaoning, China
^bInorganic Systems Engineering, Department of Chemical Engineering, Delft University of Technology, Van der Maasweg, the Netherlands
^cSchool of Materials Science and Engineering & National Institute for Advanced Materials, Nankai University, Tianjin 300350, China
^dUniversity of Chinese Academy of Sciences, Beijing 100049, China
^eBiobased Chemistry and Technology, Wageningen University & Research, the Netherlands
^fLaboratory of Organic Chemistry, Wageningen University & Research, the Netherlands

Received:2021-05-27 Revised:2021-05-27 Online:2022-03-18 Published:2022-02-18
Contact: Evgeny A. Pidko, Can Li
About author:Jijie Wang (State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences) received his Ph.D degree in 2013 from Xiamen University. From 2013 to 2017, he did postdoctoral research at Dalian Institute of Chemical Physics (DICP), Chinese Academy of Sciences, his Co-supervisor is Professor Can Li. At the beginning of 2018, he joined the DICP, where he is now a professor of DICP. His researches mainly focus on catalytic hydrogenation of carbon dioxide to methanol, low carbon olefin, aromatic hydrocarbon, etc. He has made original achievements in the catalytic hydrogenation of carbon dioxide to methanol with high selectivity and stability, and developed ZnO-ZrO₂ bimetal oxide solid solution catalyst to open up a new way for the hydrogenation of carbon dioxide. As one of the main contributors, he completed the world's first set of "liquid sunshine methanol" industrial pilot and demonstration projects. He has published 20 papers in Science Advances, Joule and other journals, applied for 14 domestic patents, and 2 international PCT patents. He has received Min Enze Energy and Chemical Industry Award-Youth Progress Award, International Catalytic Conference Young Scientist Award. He joined the editorial board of Chin. J. Catal. in 2020.
First author contact:
^† These authors contributed equally.
Supported by:
National Key R&D Program of China(2017YFB0702800);Fundamental Research Center of Artificial Photosynthesis(22088102);National Natural Science Foundation of China(21802139);Youth Innovation Promotion Association CAS(2019183)

摘要/Abstract

摘要：

近年来, 利用可再生能源分解水制氢进而开展二氧化碳资源化利用的研究引起了学术界和工业界的极大兴趣. 科学层面上它暗合了自然光合作用的理念; 应用层面上它把二氧化碳变废为宝, 既可以得到人类必需的含碳化学品, 又可以实现碳中和. 甲醇被认为是二氧化碳资源化的最佳选择, 可在动力、交通、化工等领域替代煤炭等传统化石能源, 也是良好的载氢分子, 还可作为基础原料生产烯烃、芳烃等大宗化学品. 美国南加州大学Olah教授和中国科学院顾问施春风教授曾先后提出“甲醇经济”和“液态阳光”, 系统阐述了上述理念. 针对CO₂加氢制甲醇过程, 开发高效的催化剂仍是当前亟需解决的关键技术. 目前研究较多的铜基催化剂和氧化物催化剂存在转化率和选择性难以兼顾的问题, 近期报道的钴基催化剂等又存在副产物甲烷较高的不足.
本文报道了一种全新的Cd/TiO₂催化剂, 其催化CO₂加氢的转化率达到15.8%, 甲醇选择性达到81%, 甲烷选择性控制在0.7%以下, 是目前报道的综合性能最优的催化剂之一. 实验发现, Cd在不同载体上催化性能差异极大, Cd/TiO₂表现出最佳催化性能, 单一的Cd或TiO₂几乎没有活性, 说明Cd和TiO₂产生了强烈的相互作用. TiO₂载体上Cd含量优化实验表明, 随着Cd含量增加, CO₂加氢活性和甲醇选择性均呈现上升趋势, 至3.5%含量时均达极大值; 继续增加Cd含量时, 活性和选择性略有下降. 催化剂的结构表征结果表明, 0.35%Cd/TiO₂催化剂中Cd主要以单位点形式存在, 3.5%Cd/TiO₂催化剂中Cd主要以团簇形式存在, 7%Cd/TiO₂催化剂中Cd则以单位点、团簇及纳米颗粒共存状态存在. X射线光电子能谱结果表明, 0.35%Cd/TiO₂和3.5%Cd/TiO₂催化剂中单位点Cd和团簇Cd表现为+2价, 而7%Cd/TiO₂催化剂中Cd表现为零价, 这可能是因为7%Cd/TiO₂催化剂中Cd主要以金属颗粒形式存在. X射线精细结构衍射谱结果表明, Cd团簇除了与Cd单位点相同的Cd‒O键外, 还有少量Cd‒Cd键, 从而表现出独特的电子性能. 原位红外实验表明, Cd/TiO₂催化剂上CO₂加氢经过HCOO*中间体生成甲醇, 通过DFT计算发现, TiO₂负载Cd团簇模型上CO₂加氢生成甲醇的决速步能垒只有TiO₂负载单位点Cd模型上的一半, 证明了TiO₂负载Cd团簇是催化反应的活性中心.

关键词: 二氧化碳加氢, 甲醇, 镉/二氧化钛催化剂, 镉团簇, 二氧化钛

Abstract:

The conversion of CO₂ to methanol with high activity and high selectivity remains challenging owing to the kinetic and thermodynamic limitations associated with the low chemical reactivity exhibited by CO₂. Herein, we report a novel Cd/TiO₂ catalyst exhibiting a methanol selectivity of 81%, a CO₂ conversion of 15.8%, and a CH₄ selectivity below 0.7%. A combination of experimental and computational studies revealed that the unique electronic properties exhibited by the Cd clusters supported by the TiO₂ matrix were responsible for the high selectivity of CO₂ hydrogenation to methanol via the HCOO* pathway at the interfacial catalytic sites.

Key words: CO₂ hydrogenation, Methanol, Cd/TiO₂ catalyst, Cd cluster, TiO₂

王集杰, Jittima Meeprasert, 韩哲, 王欢, 冯振东, 汤驰洲, 沙峰, 唐珊, 李冠娜, Evgeny A. Pidko, 李灿. TiO₂负载的高分散Cd团簇催化剂高效催化CO₂加氢制甲醇[J]. 催化学报, 2022, 43(3): 761-770.

Jijie Wang, Jittima Meeprasert, Zhe Han, Huan Wang, Zhendong Feng, Chizhou Tang, Feng Sha, Shan Tang, Guanna Li, Evgeny A. Pidko, Can Li. Highly dispersed Cd cluster supported on TiO₂ as an efficient catalyst for CO₂ hydrogenation to methanol[J]. Chinese Journal of Catalysis, 2022, 43(3): 761-770.

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图/表 4

Fig. 1. Catalytic performance. (a) CO2 conversion and methanol selectivity for various catalysts; (b) Catalytic performance as a function of the Cd/(Cd+Ti) molar ratio; (c) Variation in the CO2 conversion and methanol selectivity exhibited by 3.5% Cd/TiO2 under various pressures and temperatures; (d) Methanol yield and specific activity exhibited by the CuZnO, Cd/TiO2, and ZnO-ZrO2 catalysts at various temperatures. The standard reaction conditions were as follows: 2.0 MPa, H2/CO2 = 3/1, 290 °C, GHSV = 24000 mL·gcat-1·h-1.

Fig. 2. Structural characterization. (a) XRD spectra obtained from the fresh Cd/TiO2 catalysts. (b,c) XRD spectra obtained from the used Cd/TiO2 catalysts. Aberration-corrected STEM-HAADF images of the 0.35% Cd/TiO2 (d), 3.5% Cd/TiO2 (e), and 7% Cd/TiO2 (f) catalysts. The isolated Cd sites are circled in yellow, the Cd clusters are circled in red, and the Cd particles are circled in purple. (g) XPS spectra obtained from the Cd/TiO2 catalysts treated using CO2/H2 mixed gas. (h) EXAFS spectra with k3-weighted data obtained from 0.35% Cd/TiO2 and 3.5% Cd/TiO2. (i) Schematic structure illustration of the Cd/TiO2 catalysts.

Fig. 3. Surface reactivity. (a) CO2-TPD of 3.5% Cd/TiO2, TiO2, and Cd; (b) In-situ DRIFT spectra obtained from surface species formed during CO2 adsorption; (c) H2-TPD of 3.5% Cd/TiO2, TiO2, and Cd; (d) In-situ DRIFT spectra obtained from the surface species formed during the reaction for 3.5% Cd/TiO2.

Fig. 4. DFT calculations. Reaction energy profiles corresponding to CO2 hydrogenation to CH3OH in the Cd4/TiO2 and CdTiO3 catalysts via the formate pathway. (unit: eV). In the case of the Cd4/TiO2 catalyst, the species marked with an asterisk (*) and hash sign (#) interact with the TiO2 site and Cd site of the Cd4/TiO2 catalyst, respectively.

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TiO₂负载的高分散Cd团簇催化剂高效催化CO₂加氢制甲醇

Highly dispersed Cd cluster supported on TiO₂ as an efficient catalyst for CO₂ hydrogenation to methanol

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