H-assisted CO2 dissociation on PdnPt(4−n)/In2O3 catalysts: a density functional theory study,Physical Chemistry Chemical Physics

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H-assisted CO2 dissociation on PdnPt(4−n)/In2O3 catalysts: a density functional theory study
Physical Chemistry Chemical Physics ( IF 2.9 ) Pub Date : 2024-08-22 , DOI: 10.1039/d4cp02389g
Xiaowen Wang ₁ , Jiaying Pan ₁ , Haiqiao Wei _{1,

2} , Wenjia Li ₃ , Jun Zhao _{2,

4} , Zhen Hu ₁

Affiliation

CO₂ hydrogenation into valuable chemical compounds can effectively address the issues of greenhouse gas emissions and energy scarcity. The activation and dissociation processes of CO₂ are crucial for its reduction reactions, but the effects of *H adatoms on the C–O cleavage are still confusing. This study investigates the H-assisted CO₂ dissociation pathways on the Pd_nPt_(4−n)/In₂O₃ (n = 0–4) catalysts via DFT calculation. Initially, the adsorption properties of *H₂, *COOH, and *HCOO species are calculated. Then, two H-assisted CO₂ dissociation channels, i.e., *CO₂ + *H → *COOH → *CO + *OH and *CO₂ + *H → *HCOO → *CHO + *O, are studied. Results show that Pt and Pd promote the CO₂ hydrogenation and C–O bond cleavage reactions, respectively. In comparison to CO₂ direct dissociation, the COOH-mediated and HCOO-mediated channels facilitate and impede the C–O bond cleavage, respectively. Overall, the Pd₃Pt/In₂O₃ constituent is suggested for the H-assisted CO₂ dissociation reaction. The electronic effects of the Pd_nPt_(4−n) bimetals adjust the stabilities of the intermediates and barriers of the elementary steps, and the interactions between Pd_nPt_(4−n) and In₂O₃ provide extra sites for the adsorbates and reaction steps. This study reveals the effects of *H on the C–O bond dissociation processes and provides useful insight into designing PdPt/In₂O₃ catalysts for CO₂ hydrogenation reactions.

中文翻译：

PdnPt(4−n)/In2O3 催化剂上 H 辅助 CO2 解离：密度泛函理论研究

CO ₂加氢成有价值的化合物可以有效解决温室气体排放和能源短缺问题。 CO ₂的活化和解离过程对其还原反应至关重要，但*H吸附原子对C-O裂解的影响仍然令人困惑。本研究通过DFT 计算研究了Pd _n Pt _{(4− n )} /In ₂ O ₃ ( n = 0–4) 催化剂上H 辅助的CO ₂解离途径。首先，计算*H ₂ 、*COOH和*HCOO物质的吸附性质。然后，研究了两种H辅助的CO ₂解离通道，即*CO ₂ + *H→*COOH→*CO + *OH和*CO ₂ + *H→*HCOO→*CHO + *O。结果表明Pt和Pd分别促进CO ₂加氢和C-O键断裂反应。与CO ₂直接解离相比，COOH介导和HCOO介导的通道分别促进和阻碍C-O键裂解。总体而言，建议将Pd ₃ Pt/In ₂ O ₃成分用于H辅助CO ₂解离反应。 Pd _n Pt _{(4− n )}双金属的电子效应调节基本步骤的中间体和势垒的稳定性，Pd _n Pt _{(4− n )}和 In ₂ O ₃之间的相互作用为吸附物提供了额外的位点和反应步骤。这项研究揭示了 *H 对 C-O 键解离过程的影响，并为设计用于 CO ₂加氢反应的 PdPt/In ₂ O ₃催化剂提供了有用的见解。

更新日期：2024-08-27

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