Aug 2026· Angewandte Chemie· pp.
e1543450
· 0 citations· 37 references
Medicine
Abstract
Product formation is commonly regarded as the endpoint of heterogeneous catalysis, yet the subsequent fate of products near active surfaces critically affects catalytic turnover. For syngas-to-methanol conversion over Cu/Zn/Al (CZA) catalysts, product retention and re-adsorption represent an underappreciated limitation governing both activity and selectivity. Methanol generated at metal-oxide interfaces tends to remain near active sites, where interactions with surface hydroxyls trigger secondary reactions such as the water-gas shift. By physically mixing commercial CZA with hydrogen-bond-rich porous frameworks, we introduce a non-covalent host-guest extraction pathway that captures methanol from the interfacial region and facilitates its release into the gas phase. This extraction shifts the local adsorption-desorption equilibrium, suppresses methanol re-adsorption, and boosts methanol space-time yield by 1.12-1.43 times relative to pristine CZA, while retaining > 92.3% selectivity. In situ spectroscopy, transient kinetics, and simulations confirm the porous framework acts as a molecular sink, regulating methanol residence time and transport without direct catalytic participation. This effect is general across distinct metal-organic and covalent organic frameworks, establishing non-covalent extraction as a transferable strategy. This work demonstrates that non-covalent control of product desorption and transport serves as a complementary design principle for heterogeneous catalysis beyond conventional active-site engineering.
Metal-oxide interfaces (MOI) are pivotal in heterogeneous catalysis due to their unique interfacial properties. This review focuses on their applications in selective alcohol oxidation, environmental catalysis (e.g., CO oxidation, soot combustion), CO2 hydrogenation, dry reforming of methane (DRM), and alkane conversion. Research demonstrates that MOI effectively modulates catalytic performance. The advantages of MOI can be generally described as follows: (1) mitigates competitive adsorption to enhance catalytic activity; (2) simultaneously activates two reactants through strong metal-support interactions; (3) stabilizes nanoparticles against sintering under harsh reaction conditions. This review systematically summarizes MOI construction strategies and structure-performance relationships, aiming to provide a theoretical foundation and practical guidance for the rational design of high-performance, stable heterogeneous catalysts.
Mengqi Wu, Mengtao Huang, Kun Liu et al.· Chemistry· 0 citations
Cu-based catalysts are promising for CO2-to-methanol conversion, but their activity and stability are usually compromised by the accumulation of byproduct water. Although physically mixing hydrophobic additives with Cu-based catalysts can facilitate water removal, how to regulate the water-removal kinetics in this process, as well as its impact on the reaction kinetics of CO2 hydrogenation to methanol, remains insufficiently understood. Herein, by modifying the polydivinylbenzene (PDVB) with porosity, we regulate the surface hydrophobicity of its mixture with a layered double hydroxide (LDH)-derived CuZnAlMg catalyst, thereby enhancing the water removal kinetics on the mixed catalyst surface. In contrast to nonporous PDVB, porous PDVB, with a substantially higher surface area and abundant mesopores, effectively creates additional H2O transfer channels. This facilitates rapid water removal, which in turn inhibits the oxidation of Cu nanoparticles and ensures the re-exposure of oxygen-vacancy active sites for sustained catalysis. Furthermore, water removal also accelerates the formation and subsequent hydrogenation of intermediates for higher activity. Consequently, a high space-time yield of methanol of 519.89 gMeOH kgcat–1 h–1 and a CO2 conversion rate of 26.35% are achieved at 5 MPa and 260 °C. The mixed catalyst exhibits excellent stability over 200 h of continuous operation. This work offers a simple yet robust strategy for regulating catalyst hydrophobicity toward efficient CO2 hydrogenation to methanol.
Zhefeng Li, Jun Cheng, Yunshuyu Sun et al.· Energy & Fuels· 0 citations
The rational design of metal-acid bifunctional catalysts is critical for tandem catalysis. However, the precise control of intermediate formation and conversion remains challenging due to indiscriminate reactant access to both metal and acid centers. Herein, we utilize the steric hindrance of the sodalite (SOD) framework to exclude bulky benzene and cyclohexene from accessing the metal sites, confining intermediate cyclohexene formation and conversion exclusively to acidic domains and breaking the conventional competitive pathway of cyclohexene migration from metal to adjacent acid sites. Experimentally, Ru nanoparticles were confined within the SOD framework (Ru@SOD), and distal acid sites were introduced by mixing with HY zeolite. In-depth studies reveal that coupled hydrogenation-alkylation reactions over HY domains drive a hydrogen pump effect, which continuously draws active hydrogen spillover from encapsulated Ru sites to sustain efficient benzene hydroalkylation. Such isolated metal-acid architecture redirects the pathway from a competitive hydrogenation/alkylation to an acid-driven alkylation mediated by hydrogen spillover. At ∼40% benzene conversion, 75.6% cyclohexylbenzene (CHB) selectivity and a record-high 47.3% CHB yield were achieved with the Ru@SOD + HY catalyst, significantly outperforming reference samples and other catalysts reported to date. This work provides a universal spatial isolation of metal-acid sites to modulate intermediate evolution and optimize selectivity in complex tandem catalysis.
Electrochemical CO2 reduction offers a route to produce liquid fuels such as methanol; however, strong competition from hydrogen evolution and limited control over key reaction intermediates lead to low single‐product selectivity and poor stability under operating conditions. Heteronuclear dual‐atom catalysts (DACs) have shown great promise in this regard because two neighboring catalyst atoms can cooperatively bind and polarize oxygenated intermediates. Despite these attractive features, DACs often struggle to stabilize the right early intermediate for methanol, so CO2 protonation defaults back to *COOH (and then *CO), which breaks methanol selectivity. Here, we utilize DAC systems stabilized on a carbon nitride (C3N4) framework to resolve this mechanistic bottleneck at the molecular level using density functional theory and constrained molecular dynamics simulations. A Sn–N2/Cu–N2 DAC embedded in a C3N4 framework, coupled to an explicit aqueous interface and evaluated under an applied potential, is shown to favor methanol formation through a six‐electron *OCHO pathway. The neighboring Sn and Cu sites synergistically stabilize a bidentate *OCHO intermediate through Sn─O p‐orbital interactions, while suppressing formation of *COOH. The results provide a clear design rule for methanol‐selective CO2RR: enforce cooperative bidentate binding that locks in *OCHO and redirects the first protonation step away from *COOH and toward methanol.
Imran Muhammad, Danish Khan, Tanveer Hussain et al.· Small Methods· 0 citations
Aqueous-phase reforming (APR) of biomass-derived effluent is an attractive route to renewable hydrogen, yet real, acid-rich streams reform poorly and rapidly deactivate the commercial catalysts. Herein, we propose a rational catalyst design strategy involving Pt atoms anchored on nitrogen-doped carbon and interfaced with ZnO domains. The developed catalyst (HD-PtN/ZnO/C) features highly dispersed Pt as C-C activation sites; Lewis-acidic ZnO to enhance the inner water-gas shift (WGS) reaction; N-induced locally alkaline microenvironment that facilitates the adsorption and activation of acidic substrates, successfully establishing a synergistic system. The design enables nearly a complete conversion of the mixed aliphatic acids effluent, corresponding to TOFH2 as 5288 h-1, 3.4 times higher than that from the commercial Pt/C catalyst. N-doping not only facilitates an excellent hydrogen yield (61.3 mmolH2 gTOC-1) but also contributes significantly to the stability of Pt and ZnO species. This catalyst represents a breakthrough by simultaneously maintaining high APR activity and catalyst structural stability in a real acidic effluent system. Sustainability tests showed activity can be fully recovered by a mild 300 °C calcination, enabling at least five cycles. This work paves the way for an efficient and durable hydrogen production from acidic industrial wastewater and expands the applications of single-atom catalysts.
Reactive metal-support interactions (RMSIs) frequently occur under high-temperature reaction conditions, leading to intricate reconstructions of metal-oxide interfaces and alloy formation. Such uncontrollable features severely impede the optimization of catalytic performance. In this study, we demonstrate precise control over RMSIs by leveraging the high mobility of InOx on CeO2 support under hydrogen reducing conditions-directly visualized by in situ environmental electron microscopy-in combination with the quantitative tuning of InOx content via atomic layer deposition. The resulting optimized catalyst delivers an exceptional space-time yield of 1.67 gMeOH·gcat -1·h-1 at 280°C in the CO2 hydrogenation reaction, surpassing previously reported Ni-based catalysts and even Pd-based noble metal catalysts in the literature. In situ spectroscopic characterization reveals that the controlled RMSIs enables the optimization of InOx/NiIn interface, which promotes the selective conversion of HCOO* to CH3O* and subsequently to methanol, thereby significantly enhancing the methanol production. These findings highlight the critical role of precisely regulated RMSIs in the rational design of high-performance catalysts.
Qimeng Sun, Xinyu Liu, Yang Liu et al.· Angewandte Chemie· 0 citations
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