Surface-Modified S═O Microenvironment Boosts Catalyzed Oxidation of Alcohol <i>via</i> Hydrogen Bond Interactions

Feng, Xiao; Shi, Song; Zhu, Guozhi; Wang, Yinwei; Cao, Jieqi; Xu, Jie

doi:10.1021/acscatal.3c04779

Cited by 3 publications

(1 citation statement)

References 62 publications

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“…The adjacent proton in Brønsted acid-redox site pairs provides additional “confinement” to the unconfined redox sites on H 3 PMo- fresh clusters, thus stabilizing the [OH···HOCH 2 ···H···O*] ‡ transition state by 50 kJ mol –1 in apparent activation enthalpy, accompanied by 97 J mol –1 K –1 more apparent activation entropy loss. The mechanistic origins of the reactivity enhancement in methanol ODH similar to those found in Brønsted acidic zeolite-catalyzed reactions in nature, , and similar adjacent species-induced reactivity promotion has been reported in various reactions, e.g., alkane cracking in extra-framework silica species grafted H-MFI, and in extra-framework alumina species grafted H-MFI , and H-ZSM-5, as well as alcohol dehydrogenation in SO groups modified encapsulated AuPd alloys …”

Section: Results and Discussionmentioning

confidence: 99%

Catalytic Consequences of Protons in Methanol Oxidative Dehydrogenation on Molybdenum-Based Polyoxometalate Clusters

Cai,

Chin

2024

ACS Catal.

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This study unravels the catalytic effects of adjacent protons in redox catalysis of bifunctional Keggin-type phosphomolybdic acid clusters (H3PMo12O40). Isolated redox sites (O*) and Brønsted acid-redox site pairs (OH/O*) catalyze methanol oxidative dehydrogenation (ODH), a redox reaction, via the identical elementary steps and the formation of the kinetically relevant [HOCH2···H···O*]‡ and [OH···HOCH2···H···O*]‡ transition states, but with different kinetic requirements, established from selective site inactivation, product tracking, dynamic pyridine/2,6-di-tert-butylpyridine titrations, and kinetic assessments. The presence of adjacent protons interacts with and stabilizes the methanol precursor in the OH···HOCH2–H···O* adsorbed state through additional H-bonding interactions by 57 kJ mol–1 in adsorption enthalpy and by 144 J mol–1 K–1 in adsorption entropy. These additional interactions, stabilizing the [OH···HOCH2···H···O*]‡ transition state, lead to a decrease in apparent methanol activation enthalpy of 50 kJ mol–1 and in activation entropy of 97 J mol–1 K–1, resulting in an overall increase in methanol ODH turnovers. The kinetic consequences of protons established here enable the rationalization of the redox reactivity on bifunctional POM clusters and display a nontraditional confinement effect to stabilize transition state energies.

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Section: Results and Discussionmentioning

confidence: 99%

Catalytic Consequences of Protons in Methanol Oxidative Dehydrogenation on Molybdenum-Based Polyoxometalate Clusters

Cai,

Chin

2024

ACS Catal.

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Deep P‐C Interface Reconstruction for High‐Performance Potassium Storage

Chen,

Deng,

Guo

et al. 2024

Adv Funct Materials

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Potassium‐ion batteries (PIBs) capable of achieving full charge in minutes, or even in seconds, while maintaining high energy densities, are highly desirable for practical applications. However, significant challenges exist in developing electrodes that can sustain both high capacity and rapid charging rates. Conventional phosphorus‐carbon composites, limited by the intrinsic common carbon materials structure, often fail to prevent the edges reconstruction of black phosphorus (BP), thereby limiting its potential advantages as a high‐capacity, high‐rate anode. This study addresses these challenges by grafting BP onto a super‐porous carbon (SPC) framework to serve as an anode for potassium storage. The large number of open pores in SPC ensures the uniform distribution of BP nanoparticles in this carbon matrix, realizing the complete potassiation reactions and uniform volumetric strain dispersion. The abundant defects significantly promote the phosphorus‐carbon reconstruction between edge carbon atoms and edge phosphorus atoms, effectively inhibiting the P‐P edge reconstruction of BP to ensure open edges for rapid K+ diffusion. As a result, the composite exhibits excellent performance in potassium storage, demonstrating superior capacity, charging rates, and cycling durability. This research provides a new insight into enhancing BP‐base anodes, offering favorable guidance for the development of high‐performance materials.

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