原子层沉积和表面有机金属化学法制备的TiO2负载CO2加氢催化剂中钴态的光谱学探究

doi:10.1016/S1872-2067(26)65131-5

摘要/Abstract

摘要：

二氧化钛(TiO₂)是经典催化载体, 但材料自身强光吸收特性大幅衰减透射模式X射线吸收光谱(XAS)信号, 难以开展工况下原位结构-活性动态研究. 本文开发了一种结合原子层沉积(ALD)和表面有机金属化学(SOMC)的方法, 在二氧化硅基底表面沉积超薄TiO₂薄膜, 再于薄膜表面锚定钴纳米颗粒, 制备可适配透射光谱表征的Co/TiO₂-SiO₂模型催化剂. 催化性能测试结果表明, Co/TiO₂-SiO₂的CO₂甲烷化催化活性与纯TiO₂负载钴催化剂Co/TiO₂相近; 与之形成对比的是SiO₂直接负载钴材料Co/SiO₂, 该体系优先催化逆水煤气变换反应生成CO. CO₂加氢工况下原位钴K边XAS表征结果证实, 该复合催化剂中的钴物种全程维持金属零价态, 这一特征与其高甲烷化选择性完全匹配.

综上, 本工作证明ALD与SOMC复合制备策略通用性强, 为构建适配原位光谱表征的TiO₂基负载型模型催化体系提供可靠制备平台.

关键词: CO₂加氢, TiO₂-负载Co, 原子层沉积, 表面有机金属化学, X-射线吸收光谱

Abstract:

TiO₂ is ubiquitous as a support in catalytic applications. However, its highly absorptive nature hampers the use of transmission-based spectroscopic techniques such as X-ray absorption spectroscopy (XAS), limiting in-situ/operando structure-activity studies. Here, we developed a combined atomic layer deposition (ALD) and surface organometallic chemistry (SOMC) approach to synthesize cobalt nanoparticles (NPs) supported on a TiO₂ thin film dispersed on SiO₂, yielding a spectroscopically accessible Co/TiO₂-SiO₂ model catalyst. The Co/TiO₂-SiO₂ exhibits CO₂ methanation activity similarly to Co/TiO₂ but in contrast to Co/SiO₂, which preferentially catalyzes the reverse water gas shift reaction. In-situ Co K-edge XAS during CO₂ hydrogenation conditions demonstrates that cobalt remains metallic, consistent with the observed methanation activity. This study highlights that combining ALD and SOMC provides a versatile platform for constructing TiO₂-supported model catalysts and enables their characterization via in situ spectroscopy.

Key words: CO₂ hydrogenation, TiO₂-supported cobalt, Atomic layer deposition, Surface organometallic chemistry, X-ray absorption spectroscopy

Xiaoyu Zhou, Wei Zhou, James Paterson, Jamie Southouse, Alexey Fedorov, Christoph R. Müller, Christophe Copéret. 原子层沉积和表面有机金属化学法制备的TiO₂负载CO₂加氢催化剂中钴态的光谱学探究[J]. 催化学报, 2026, 89: 402-409.

Xiaoyu Zhou, Wei Zhou, James Paterson, Jamie Southouse, Alexey Fedorov, Christoph R. Müller, Christophe Copéret. Spectroscopically probing the cobalt state in TiO₂-supported CO₂ hydrogenation catalysts derived from tailored materials via atomic layer deposition and surface organometallic chemistry[J]. Chinese Journal of Catalysis, 2026, 89: 402-409.

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Scheme 1. Schematic representation of a protocol for the SOMC-based synthesis of cobalt NPs supported on an ALD-derived TiO2 thin film with SiO2 as a bulk phase: ALD deposition of TiO2 via pulsed cycles of TDMAT/H2O (a), grafting of Co(CH2tBu)2tmeda (b), and H2 treatment for the Co NPs formation (c).

Fig. 1. Optimization of the TDMAT deposition on SiO2-500 followed by FTIR spectroscopy (a), calcination of TDMAT6-SiO2-500 at different temperatures (b), STEM-EDX of TiO2-SiO2-350 showing Si and Ti mappings in red and green, respectively (c).

Fig. 2. (a) FTIR spectra of the SOMC-based preparation of Co/TiO2-SiO2. Particle size distribution obtained by HAADF-STEM (b), and HAADF-STEM micrographs (c) of Co/TiO2-SiO2 and EDX mappings (d-f) of Co (blue), Ti (red), and Si (green) in pristine Co/TiO2-SiO2.

Fig. 3. CO2 hydrogenation on Co/TiO2-SiO2 with a contact time-dependent conversion (a) and product selectivity (b). (c) Selectivity comparison of the SOMC-deposited Co-based catalysts Co/SiO2 (“SiO2”), Co/TiO2-SiO2 (“ALD”), and Co/TiO2 (“TiO2”) compared at 3% CO2 conversion. Reaction conditions: 230 °C, 25 bar(g), CO2:H2:Ar = 1:3:1, 6-50 mL min-1.

Fig. 4. (a) Normalized Co K-edge XANES spectra for pristine and post-reaction Co/TiO2-SiO2 and reference data of metallic Co (Co foil) and Co(II) (Co(Np)tmeda@SiO2) and their respective 1st derivatives shown in (b) as green, blue, dark gray, and light gray, respectively. (c) In-situ XANES traces of Co/TiO2-SiO2 under CO2 hydrogenation conditions (230 °C, 25 bar) from light blue to dark blue traces over time on stream, along with the difference spectrum between the initial and final XANES spectra measured for a total of 2 h.

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原子层沉积和表面有机金属化学法制备的TiO₂负载CO₂加氢催化剂中钴态的光谱学探究

Spectroscopically probing the cobalt state in TiO₂-supported CO₂ hydrogenation catalysts derived from tailored materials via atomic layer deposition and surface organometallic chemistry

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