CO2 辅助丙烷在 VOx/In2O3 催化剂上的氧化脱氢：氧化还原性质和酸碱相互作用之间的相互作用,ACS Catalysis

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CO2 辅助丙烷在 VOx/In2O3 催化剂上的氧化脱氢：氧化还原性质和酸碱相互作用之间的相互作用
ACS Catalysis ( IF 11.3 ) Pub Date : 2022-09-01 , DOI: 10.1021/acscatal.2c02099
Xiao Jiang ₁ , Bar Mosevitzky Lis ₂ , Stephen C. Purdy ₃ , Sreya Paladugu ₄ , Victor Fung ₅ , Wenying Quan ₆ , Zhenghong Bao ₁ , Weiwei Yang ₁ , Yang He ₁ , Bobby G. Sumpter ₅ , Katharine Page _{3,

4} , Israel E. Wachs ₂ , Zili Wu _{1,

5}

Affiliation

在这项工作中，制备了一系列负载VO _x的In ₂ O ₃催化剂，并评估了它们对CO 2 辅助丙烷氧化脱氢（CO 2 -ODHP）的催化性能，_并与_单独的In 2 _O 3_{进行了比较。}最佳组成是在 3.4V/In ₂ O ₃（表面 V 密度为 3.4V nm ^{–2 ）上获得的，它不仅表现出比其他 V/In 催化剂和 In}₂ O ₃更高的 C ₃ H ₆选择性在异构转化条件下，还提高了反应稳定性。为了阐明催化剂的构效关系，VO _x /In ₂ O ₃催化剂通过化学吸附[NH ₃ -程序升温脱附（TPD）、NH ₃ -漫反射红外傅里叶变换光谱（DRIFTS）、CO ₂ - TPD 和 CO ₂ -DRIFTS]、H ₂-程序升温还原 (TPR)、原位拉曼光谱、紫外-可见漫反射光谱、近环境压力 X 射线光电子能谱、X 射线吸收光谱，并使用密度泛函理论进一步研究。_{在 VO x} /In ₂ O ₃催化剂中确定了 In-O-V 结构和低聚程度，它们在提高选择性和稳定性方面起着至关重要的作用。特别是，表面VO _x (i) 的存在抑制了In ₂ O ₃的深度还原，从而保持了活性，(ii) 中和了In ₂ O _{3上的过量碱度}_{，从而抑制丙烷干重整并实现更高的丙烯选择性，以及(iii)通过利用CO 2}作为软氧化剂引入参与脱氢反应的额外氧化还原位点。目前的工作通过酸碱相互作用和氧化还原性质之间的相互作用，通过所需的途径控制试剂的转化，为开发用于 CO _{2 -ODHP 的选择性、稳定和稳健的金属氧化物催化剂提供了见解。}

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CO2-Assisted Oxidative Dehydrogenation of Propane over VOx/In2O3 Catalysts: Interplay between Redox Property and Acid–Base Interactions

In this work, a series of VO_x-loaded In₂O₃ catalysts were prepared, and their catalytic performance was evaluated for CO₂-assisted oxidative dehydrogenation of propane (CO₂-ODHP) and compared with In₂O₃ alone. The optimal composition is obtained on 3.4V/In₂O₃ (surface V density of 3.4V nm^–2), which exhibited not only a higher C₃H₆ selectivity than other V/In catalysts and In₂O₃ under isoconversion conditions but also an improved reaction stability. To elucidate the catalyst structure–activity relationship, the VO_x/In₂O₃ catalysts were characterized by chemisorption [NH₃-temperature-programmed desorption (TPD), NH₃-diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), CO₂-TPD, and CO₂-DRIFTS], H₂-temperature-programmed reduction (TPR), in situ Raman spectroscopy, UV–vis diffuse reflectance spectroscopy, near-ambient pressure X-ray photoelectron spectroscopy, X-ray absorption spectroscopy, and further examined using density functional theory. The In–O–V structure and the extent of oligomerization, which play a crucial role in improving selectivity and stability, were identified in the VO_x/In₂O₃ catalysts. In particular, the presence of surface VO_x (i) inhibits the deep reduction of In₂O₃, thereby preserving the activity, (ii) neutralizes the excess basicity on In₂O₃, thus suppressing propane dry reforming and achieving a higher propylene selectivity, and (iii) introduces additional redox sites that participate in the dehydrogenation reaction by utilizing CO₂ as a soft oxidant. The present work provides insights into developing selective, stable, and robust metal-oxide catalysts for CO₂-ODHP by controlling the conversion of reagents via desired pathways through the interplay between acid–base interactions and redox properties.

更新日期：2022-09-01

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