CO2加氢催化剂Cu/ZrO2/SiO2上Zr(IV)表面位对甲醇生成速率的影响

doi:10.1016/S1872-2067(19)63348-6

催化学报 ›› 2019, Vol. 40 ›› Issue (11): 1741-1748.DOI: 10.1016/S1872-2067(19)63348-6

CO₂加氢催化剂Cu/ZrO₂/SiO₂上Zr(IV)表面位对甲醇生成速率的影响

Erwin Lam^a, Kim Larmier^a,c, Shohei Tada^a,d, Patrick Wolf^a, Olga V. Safonova^b, Christophe Copéret^a

a 苏黎世联邦理工学院化学与应用生物科学系, CH-8093 苏黎世, 瑞士;
b 保罗谢尔研究所, CH-5232 菲利根, 瑞士;
c 法国国际石油研究所, 69360 索莱兹, 法国;
d 东京大学化工系统工程系, 113-8656 东京, 日本

收稿日期:2019-01-12 修回日期:2019-03-05 出版日期:2019-11-18 发布日期:2019-09-06
通讯作者: Christophe Copéret
基金资助:
E.L., K.L., P.W., and S.T. are supported by the SCCER-Heat and Energy Storage program. We acknowledge PSI Super-XAS for beamtime and thank Dr. Maarten Nachtegaal (PSI) for assistance and ScopeM at ETH Zürich for the use of their electron microscopy facilities and Dr. Dmitry Lebedev (ETH) for TEM.

Zr(IV) surface sites determine CH₃OH formation rate on Cu/ZrO₂/SiO₂-CO₂ hydrogenation catalysts

Erwin Lam^a, Kim Larmier^a,c, Shohei Tada^a,d, Patrick Wolf^a, Olga V. Safonova^b, Christophe Copéret^a

a ETH Zürich, Department of Chemistry and Applied Biosciences, Vladimir-Prelog-Weg 1-5, CH 8093, Zürich, Switzerland;
b Paul Scherrer Institute, CH-5232 Villigen, Switzerland;
c IFP Energies Nouvelles, Rond-Point de l'échangeur de Solaize, BP3, 69360 Solaize, France;
d Department of Chemical System Engineering, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, 113-8656 Tokyo, Japan

Received:2019-01-12 Revised:2019-03-05 Online:2019-11-18 Published:2019-09-06
Contact: Christophe Copéret
Supported by:
E.L., K.L., P.W., and S.T. are supported by the SCCER-Heat and Energy Storage program. We acknowledge PSI Super-XAS for beamtime and thank Dr. Maarten Nachtegaal (PSI) for assistance and ScopeM at ETH Zürich for the use of their electron microscopy facilities and Dr. Dmitry Lebedev (ETH) for TEM.

摘要/Abstract

摘要： Cu/ZrO₂/SiO₂是有效的CO₂选择加氢制甲醇催化剂.为了理解混合氧化物基催化剂中ZrO₂的作用，在Cu和Zr的K边进行了原位X-射线吸收光谱测试.在反应条件下，Cu保持金属态，而Zr以三类配位环境的形式存在：体相ZrO₂，配位饱和的、以及不饱和的Zr （IV）表面位.配位不饱和Zr表面位可通过线性拟合参比的X射线吸收近边结构光谱进行定量，发现其数量与甲醇生成速率有关，因而表明Zr （IV） Lewis酸表面位在驱动选择生成甲醇反应中的重要性.这与提出的机理是一致的：在裂解H₂的Cu纳米颗粒与稳定反应中间体的Zr （IV）表面位之间的界面上进行CO₂加氢.

关键词: CO₂加氢, ZrO₂/SiO₂负载的Cu纳米颗粒, Lewis酸表面位, 原位X射线吸收光谱

Abstract: Cu/ZrO₂/SiO₂ are efficient catalysts for the selective hydrogenation of CO₂ to CH₃OH. In order to understand the role of ZrO₂ in these mixed-oxides based catalysts, in situ X-ray absorption spectroscopy has been carried out on the Cu and Zr K-edge. Under reaction conditions, Cu remains metallic, while Zr is present in three types of coordination environment associated with 1) bulk ZrO₂, 2) coordinatively saturated and 3) unsaturated Zr(IV) surface sites. The amount of coordinatively unsaturated Zr surface sites can be quantified by linear combination fit of reference X-Ray absorption near edge structure (XANES) spectra and its amount correlates with CH₃OH formation rates, thus indicating the importance of Zr(IV) Lewis acid surface sites in driving the selectivity toward CH₃OH. This finding is consistent with the proposed mechanism, where CO₂ is hydrogenated at the interface between the Cu nanoparticles that split H₂ and Zr(IV) surface sites that stabilizes reaction intermediates.

Key words: CO₂ hydrogenation, ZrO₂/SiO₂ supported Cu nanoparticles, Lewis acidic surface sites, In situ X-ray absorption spectroscopy

Erwin Lam, Kim Larmier, Shohei Tada, Patrick Wolf, Olga V. Safonova, Christophe Copéret. CO₂加氢催化剂Cu/ZrO₂/SiO₂上Zr(IV)表面位对甲醇生成速率的影响[J]. 催化学报, 2019, 40(11): 1741-1748.

Erwin Lam, Kim Larmier, Shohei Tada, Patrick Wolf, Olga V. Safonova, Christophe Copéret. Zr(IV) surface sites determine CH₃OH formation rate on Cu/ZrO₂/SiO₂-CO₂ hydrogenation catalysts[J]. Chinese Journal of Catalysis, 2019, 40(11): 1741-1748.

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CO₂加氢催化剂Cu/ZrO₂/SiO₂上Zr(IV)表面位对甲醇生成速率的影响

Zr(IV) surface sites determine CH₃OH formation rate on Cu/ZrO₂/SiO₂-CO₂ hydrogenation catalysts

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