Insights into the Influence of CeO2Crystal Facet on CO2Hydrogenation to Methanol over Pd/CeO2Catalysts

催化作用 面(心理学) 密度泛函理论 甲醇 氧气 空位缺陷 材料科学 金属 Crystal(编程语言) 化学 纳米颗粒 结晶学 化学工程 纳米技术 计算化学 有机化学 心理学 计算机科学 冶金 工程类 程序设计语言 人格 社会心理学 五大性格特征
作者
Feng Jiang,Shanshan Wang,Bing Liu,Jie Liu,Li Wang,Yang Xiao,Yuebing Xu,Xiaohao Liu
出处
期刊:ACS Catalysis [American Chemical Society]
卷期号:10 (19): 11493-11509 被引量:674
标识
DOI:10.1021/acscatal.0c03324
摘要

CeO2 is an excellent potential material for CO2 hydrogenation attributed to the highly tunable properties including metal–support interaction and abundant oxygen vacancy. In this work, four CeO2 supports with structurally well-defined different shapes and crystal facets are hydrothermally prepared, and their effects on the composition of Pd species and oxygen vacancy over Pd/CeO2 catalysts have been intensively investigated in the reduction of CO2 to methanol. The 2Pd/CeO2-R (rods) shows the highest concentration and number of oxygen vacancies, where the (110) facet with high surface oxygen mobility and low oxygen vacancy formation energy is exposed over the CeO2-R surface. The oxygen mobility at the interface of (111) and (100) facets mainly observed on 2Pd/CeO2-P (polyhedrons) is higher than the single (111) and (100) facets mainly observed on 2Pd/CeO2-O (octahedrons) and 2Pd/CeO2-C (cubs), respectively. The presence of Pd highly promotes the formation of oxygen vacancies by providing dissociated H atoms to facilitate the removal of surface O in ceria support under a H2 atmosphere. Both the PdxCe1–xOδ solid solution dominated on CeO2-R and the PdO species dominated on CeO2-O are reduced to metallic Pd after reduction with 6–10 nm average particle size. As revealed by density functional theory (DFT) calculations, in contrast to the single Pd0 atom on CeO2 and the thermodynamically most unstable PdxCe1−xOδ solid solution, the Pd0 nanoparticles are the most stable species under the realistic reaction conditions. The 2Pd/CeO2-R shows the highest catalytic activity as the abundantly available oxygen vacancies function as CO2 adsorption and activation sites. Moreover, oxygen vacancy reactivity is correlated with its formation energy. The lower formation energy facilitates the formation of oxygen vacancy; however, the reactivity of each oxygen vacancy is lower as the TOFoxygen vacancy of 2Pd/CeO2-O is 15 times as that of 2Pd/CeO2-R. Thus, a suitable oxygen vacancy formation energy is likely favorable for enhancing CO2 reactivity. DFT calculations indicate that the CH3OH formation is most probably from the formate (HCOO*) pathway via the C–O bond cleavage in H2COOH*, with the reduction of HCOO* to HCOOH* as the rate-limiting step. These results would provide experimental and theoretical insights into the rational design of an effective catalyst for CO2 hydrogenation.
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