Xianfeng Yi

The selective oxidation of methane to value‐added oxygenates under mild conditions is hindered by its inert C‐H bond and the over‐oxidation. Herein, we report a dual‐modification strategy combining gallium incorporation with alkaline hydrothermal treatment to enhance Fe dispersion and tailor acidity in a Silicalite‐1 zeolite. The resulting 0.5Fe/Ga‐S‐1‐Hydrothermal Treatment (HTS) catalyst delivers a formic acid (FA) yield of 58,851 μmol g _cat ⁻¹ h ⁻¹ with 90.3% liquid‐product selectivity at 70°C using H ₂ O ₂ as the oxidant, cycling stability. Characterizations reveal that Ga doping promotes moderate acid sites, while alkaline treatment drives the redispersion of aggregated iron oxide clusters into dispersed, isolated extra‐framework Fe ³⁺ species, the key active centers. Electron paramagnetic resonance and in situ Fourier Transform Infrared Spectroscopy (FTIR) support a radical‐mediated pathway involving ·OH, ·OOH, and ·CH ₃ intermediates drive the oxidation of methane to FA. This work demonstrates that integration of heteroatom doping and post‐synthetic treatment offers a platform for designing high‐performance zeolite catalysts for methane valorization.

The zeolite‐catalyzed dehydration of low‐carbon alcohols is a crucial step in the conversion of biomass‐derived compounds. Compared to methanol and ethanol, the propanol dehydration mechanism remains poorly understood. The core challenge lies in the high reactivity and short lifetime of its intermediates, beyond the time‐resolution of conventional spectroscopic techniques. In this work, we proposed an ammonia co‐adsorption strategy to concurrently decelerate the reaction rate and capture the active intermediates during zeolite‐catalyzed iso ‐propanol dehydration process. In combination with one‐/two‐dimensional solid‐state NMR and theoretical simulations, we successfully resolved the long‐standing controversy on the origin and evolution of the highly reactive iso ‐propyl alkoxy or carbocation intermediates. It is found that the formation sequence of these active species and propene is closely associated with the zeolite topological architectures, exhibiting a hitherto unreported topology‐dependence. These findings provide a reliable strategy for elucidating the detailed mechanism of the extremely quick alcohol dehydration reaction and offer new mechanistic insights into the zeolite‐catalyzed alcohol chemistry.

The zeolite‐catalyzed dehydration of low‐carbon alcohols is a crucial step in the conversion of biomass‐derived compounds. Compared to methanol and ethanol, the propanol dehydration mechanism remains poorly understood. The core challenge lies in the high reactivity and short lifetime of its intermediates, beyond the time‐resolution of conventional spectroscopic techniques. In this work, we proposed an ammonia co‐adsorption strategy to concurrently decelerate the reaction rate and capture the active intermediates during zeolite‐catalyzed iso ‐propanol dehydration process. In combination with one‐/two‐dimensional solid‐state NMR and theoretical simulations, we successfully resolved the long‐standing controversy on the origin and evolution of the highly reactive iso ‐propyl alkoxy or carbocation intermediates. It is found that the formation sequence of these active species and propene is closely associated with the zeolite topological architectures, exhibiting a hitherto unreported topology‐dependence. These findings provide a reliable strategy for elucidating the detailed mechanism of the extremely quick alcohol dehydration reaction and offer new mechanistic insights into the zeolite‐catalyzed alcohol chemistry.

Although technologically promising for producing petrochemicals directly from renewable resources, CO2 hydrogenation to methanol remains a formidable challenge due to the activity-selectivity trade-off. Current industrial copper-based catalysts often generate substantial CO byproducts that limit CO2 utilization efficiency. Herein, we report a highly active and selective Cu/amorphous ZrO2 (Cu/a-ZrO2) catalyst by using a modified solvothermal method, which achieves a space-time methanol productivity of up to ∼1560 gmethanol kgcat–1 h–1 with a high methanol selectivity of ∼76% at 260 °C. The strategic integration of in situ synchrotron-based vacuum ultraviolet photoionization mass spectrometry (SVUV-PIMS), multimodal in situ/operando infrared spectroscopies, kinetic isotope experiments, and computational studies collectively demonstrate that the direct dissociation of C–O bond in CO2 generates *CO followed by subsequent hydrogenation to methanol via relay catalysis on adjacent Cu+–ZrOx and Cu0 dual sites, which subsequently promote the initial activation step of CO2 and the subsequent hydrogenation steps of *CO to methanol, respectively. We confirm that methanol synthesis follows a *CO-mediated mechanism on these sites, highlighting the origin of the excellent performance of self-designed Cu/a-ZrO2.

Direct hydrogenation of CO₂ to synthetic fuels and olefins using renewable hydrogen remains challenging owing to the scarcity of low-cost, active, and highly selective catalysts. Current catalytic systems often exhibit either excessive CO selectivity or generate substantial alkanes to cause a low olefin-to-paraffin (O/P) ratio that limits hydrogen utilization efficiency. Herein, we report an unsaturated ZrO_x-modified iron catalyst (Na-Fe/a-ZrO₂) that delivers an olefin selectivity exceeding 80% among organic products, while suppressing the combined CO+CH₄ selectivity to below 25% and raising the O/P ratio to as high as ∼28. Multimodal in situ/operando spectroscopies and synchrotron-based vacuum ultraviolet photoionization mass spectrometry (SVUV-PIMS) demonstrate that unsaturated ZrO_x sites can modulate the activation modes of surface-bound *CO intermediates and selectively promote *CO insertion into alkyl species. This process consumes reactive intermediates that would otherwise desorb to form undesirable byproducts, thereby enabling selective olefin synthesis compatible with hydrogen-efficient CO₂ conversion.

The activation of light alkanes on zeolites has long been attributed to strong Brønsted acid sites (BAS), a focus that has constrained further catalyst development. Here, we report that in steamed ZSM‐5 zeolites, B ₂ sites from partial hydrolysis of framework aluminum cooperate with neighboring classical BAS (B ₁ ) to establish a proximate acid‐site microenvironment that substantially enhances both alkane adsorption and activation. Combining solid‐state NMR, in situ FTIR spectroscopy with two‐dimensional correlation analysis, and density functional theory calculations, we demonstrate that the neighboring B ₁ /B ₂ sites exhibit a stronger intrinsic affinity for propane than isolated B ₁ sites, accelerating its accumulation within the pores, which is attributable to the locally optimized van der Waals interactions tuned by the Al─OH of B ₂ . The resulting cooperative acid sites synergistically entrap alkane molecules and facilitate C─H bond activation, boosting propane conversion from 27.2% to 37.5%. Our findings reveal a mechanism for alkane activation that is driven by proximate acid‐site cooperativity rather than conventional acid strength of isolated BAS, opening an avenue for designing efficient zeolite catalysts via microenvironment engineering.

The activation of light alkanes on zeolites has long been attributed to strong Brønsted acid sites (BAS), a focus that has constrained further catalyst development. Here, we report that in steamed ZSM‐5 zeolites, B ₂ sites from partial hydrolysis of framework aluminum cooperate with neighboring classical BAS (B ₁ ) to establish a proximate acid‐site microenvironment that substantially enhances both alkane adsorption and activation. Combining solid‐state NMR, in situ FTIR spectroscopy with two‐dimensional correlation analysis, and density functional theory calculations, we demonstrate that the neighboring B ₁ /B ₂ sites exhibit a stronger intrinsic affinity for propane than isolated B ₁ sites, accelerating its accumulation within the pores, which is attributable to the locally optimized van der Waals interactions tuned by the Al─OH of B ₂ . The resulting cooperative acid sites synergistically entrap alkane molecules and facilitate C─H bond activation, boosting propane conversion from 27.2% to 37.5%. Our findings reveal a mechanism for alkane activation that is driven by proximate acid‐site cooperativity rather than conventional acid strength of isolated BAS, opening an avenue for designing efficient zeolite catalysts via microenvironment engineering.

Zeolites are essential solid acid catalysts whose catalytic performance is determined by the nature of their acid sites. Conventionally, these sites are viewed as static, predetermined structural motifs, characterized by metrics such as acid type (Brønsted/Lewis), strength, and spatial distribution within a rigid framework. Emerging insights, however, reveal that acid sites are dynamic and adaptive entities. Their local structure and chemical properties can be continuously reshaped by guest molecules, particularly in working catalysts where pores are occupied by reactants, intermediates, and products. This adsorbate-induced structural reconfiguration governs key steps in catalysis, including reactant adsorption and activation, intermediate stabilization, and thus ultimate activity and selectivity. Solid-state nuclear magnetic resonance (SSNMR) spectroscopy stands out as a unique and powerful technique for resolving these dynamic processes by translating subtle host-guest interactions into atomic-scale observables. This Perspective highlights recent SSNMR advances that uncover dynamic coordination states, map adaptive catalytic microenvironments, and establish direct correlations between these dynamic features and catalytic performance. These insights are reshaping fundamental understanding in zeolite chemistry and opening new avenues for the rational design of zeolite catalysts. We conclude by outlining key challenges and future opportunities for SSNMR in advancing the molecular-level understanding and optimization of catalysts under realistic reaction conditions.

A systematic characterization of acid–base pairs in solid catalysts was conducted using advanced two-dimensional homonuclear or heteronuclear correlation solid-state nuclear magnetic resonance spectroscopy in combination with probe molecules.

Which came first, the chicken or the egg? This age-old riddle is also present for the formation sequence of the surface methoxy species and dimethyl ether in zeolite-catalyzed methanol chemistry due to their inevitable interconversion at high temperatures. The challenge is the lack of feasible reaction conditions to achieve the formation of surface methoxy species by Brønsted acids at mild temperatures. This work proposes a microenvironment design strategy to manipulate the reaction routes inside zeolite channels with the assistance of nitromethane, realizes the surface methoxy species generation catalyzed by Brønsted acids at 363 kelvin, and solves the long-standing problem of the origin and evolution of the highly active surface methoxy species during zeolite Brønsted-acid-catalyzed methanol conversion process. It is found that the surface methoxy species mainly originate from dimethyl ether decomposition under these mild conditions. These findings provide a perspective to subtly manipulate the reaction routes by tailoring the chemical microenvironment, and offer fresh insights into the zeolite-catalyzed methanol chemistry.