Theoretical insights and predictions: Photocatalytic functionalization of C(sp3)-H bonds in methane using [W10O32]4-

IF 6.5 1区 化学 Q2 CHEMISTRY, PHYSICAL
Yu-Jiao Dong, Bo Zhu, Zhong-Min Su, Wei Guan
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引用次数: 0

Abstract

Methane activation catalyzed by [MW9O32]n- (n = 3–5) and [MW5O19]m- (m = 1–3) was investigated through Density Functional Theory (DFT) calculations. We identified the key active species, active site, and reaction mechanism by studying the model reaction of methane hydroalkylation catalyzed by [W10O32]4-. Systematic comparisons across modified polyoxometalates (POMs) revealed multiple electronic and structural descriptors governing methane activation efficiency. A key discovery involves the role of photoinduced surface-bridging oxygen holes in [W10O32]4-, which serve as active sites for cleaving the inert C(sp3)Abstract ImageH σ-bond. While other POMs, including [W6O19]2-, [PW12O40]3-, and [P2W18O62]⁶ --, also exhibit methane-activating oxygen holes, their requirement for higher-energy UV excitation (compared to the visible-light-responsive [W10O32]4-) likely explains the latter’s broader utility in organic synthesis. Electronic structure analysis uncovered a near-linear correlation between triplet POM β-LUMO energies and C(sp3)Abstract ImageH activation barriers. Crucially, the negative charge density of POMs inversely regulates β-LUMO energetics: lower anionic charges correspond to reduced β-LUMO energy levels and consequently lower activation barriers. This structure–activity relationship implies that strategic charge modulation in POM architectures can fine-tune frontier molecular orbital levels, thereby controlling catalytic performance in methane functionalization. Based on these principles, we propose the low-charge metal-substituted POM [ReW5O19]- as a promising candidate for XAbstract ImageH bond activation (X = S, C, N, O).

Abstract Image

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来源期刊
Journal of Catalysis
Journal of Catalysis 工程技术-工程:化工
CiteScore
12.30
自引率
5.50%
发文量
447
审稿时长
31 days
期刊介绍: The Journal of Catalysis publishes scholarly articles on both heterogeneous and homogeneous catalysis, covering a wide range of chemical transformations. These include various types of catalysis, such as those mediated by photons, plasmons, and electrons. The focus of the studies is to understand the relationship between catalytic function and the underlying chemical properties of surfaces and metal complexes. The articles in the journal offer innovative concepts and explore the synthesis and kinetics of inorganic solids and homogeneous complexes. Furthermore, they discuss spectroscopic techniques for characterizing catalysts, investigate the interaction of probes and reacting species with catalysts, and employ theoretical methods. The research presented in the journal should have direct relevance to the field of catalytic processes, addressing either fundamental aspects or applications of catalysis.
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