TITLE: Engineering Earth-Abundant Metal Catalysts using Metal-Organic Frameworks (MOFs) for Selective Oxidation of Methane and other Hydrocarbons

Review Aug 2026

MOF-based catalysts for VOC oxidation: thermocatalysis, photocatalysis, and photothermal catalysis.

Volatile organic compounds (VOCs) are major precursors of ozone and fine particulate matter, posing significant risks to both environmental quality and human health. Catalytic oxidation is widely regarded as one of the most effective approaches for VOC abatement; however, the rational design of efficient catalysts remains a central challenge. In this review, we present a perspective on MOF-based catalysts by addressing three fundamental questions in catalyst design: where the active sites are located, how they function, and how their stability can be maintained. We show that metal-organic frameworks (MOFs), owing to their tunable coordination environments and porous architectures, provide unique opportunities to precisely define and regulate active sites. Early studies focus on dispersing active species on MOFs to control their location, while subsequent advances emphasize interfacial and electronic regulation to improve catalytic function. More recently, MOF-derived catalysts and photothermal systems have been developed to enhance structural stability and enable efficient energy utilization. By integrating representative studies from the literature with our own contributions, we review how MOF-based systems evolve from simple active-site carriers to structurally and functionally integrated catalysts. This perspective provides a unified framework for understanding structure-function-stability relationships in VOC oxidation and offers guidance for the design of next-generation catalytic systems.

Shuchen Liu, Qinye Fang, Jin-Ming Luo et al. · Chemical Communications · 0 citations

Review Aug 2026

Co‐Based Molecular Water Oxidation Catalysts: Structural Modulation and Ligand Engineering Strategies

Efficient catalysts for water oxidation are important in the development of artificial photosynthesis. Although noble metal catalysts show excellent catalytic performance and stability, their scarce availability and high cost have restricted their further practical application. Accordingly, Co‐based molecular catalysts are currently the focus of very intense research as highly appealing earth‐abundant alternatives. This review highlights a systematic consideration of their design principles, with emphasis on two major factors: nuclearity (mono‐, di‐, and multinuclear architectures) manipulation, and ligand engineering. The nuclearity dictates the catalytic framework, the degree of metal–metal cooperativity, and the catalytic mechanism. The ligands are intended to function as stabilizing high‐valent intermediates, promoting electron/proton transfer and thereby enhancing efficiency through fine electronic, steric, and redox‐active tuning. By connecting these features, this review establishes a consistent structure–activity relationship and offers perspectives on the design of robust and high‐performance Co‐based molecular catalysts for sustainable energy conversion.

Xuhui Huang, Jiangming Liu, Jingtian Hu et al. · ChemNanoMat · 0 citations

Review Open access Aug 2026

A comprehensive review on oxygen defect rich catalysts for low-temperature CO2 hydrogenation to methane and alcohols

The thermo-catalytic hydrogenation of greenhouse gas CO2 into more valuable products, primarily fuels such as methane and alcohols, is a promising pathway of carbon utilization. Since CO2 is known for its inertness with high activation energy, which makes it difficult to activate for the hydrogenation reaction, thus demanding higher temperatures for its conversion to useful products. Widespread efforts have been made to optimize catalysts for better catalytic performance at less severe operating conditions. This has garnered research community interest in utilizing the oxygen defect-rich metal catalysts, where missing oxygen atoms, or oxygen vacancies (VOs), contribute to the adsorption and geometry distortion of CO2, easing its reaction with H2. This review presents an overview of the potential of oxygen defect-rich catalysts for low-temperature CO2 hydrogenation, particularly focusing on those with supports such as CeO2, ZrO2, and TiO2. The fundamentals of VOs, including their types, impact, formation, and characterization techniques, are discussed, followed by an examination of their role in improving catalytic performance and steering reaction pathways towards methane and alcohols. Emphasis is placed on relevant optimization parameters, including catalyst features (metal loading and dispersion, type of metal, structure, etc.), presence and density of VOs and hydrogenation promoters, and reaction conditions (temperature, pressure, H2:CO2 feed ratio, flow rate). Recent advances are summarized, and lastly, current challenges and prospects are discussed.

Rahma Merza Hasan, Omar Mohamed Abdelsalam, A. Rawat et al. · Discover Nano · 0 citations

Review Open access Sep 2026

Copper-Based Bimetallic Catalysts for CO2 Hydrogenation to Methanol: Interfacial Synergy, Reaction Pathways, and Rational Design

CO2 hydrogenation to methanol is a key route for carbon recycling within the carbon capture, utilization, and storage (CCUS) framework. Cu-based catalysts are widely employed because of their low cost and high methanol selectivity, yet monometallic Cu suffers from sintering, limited CO2 activation, and competing reverse water-gas shift (RWGS) reactions. This review systematically summarizes recent advances in Cu-based bimetallic catalysts, categorized as Cu-p-block, Cu-noble metal, Cu-transition metal, and Cu-rare-earth metal systems. Throughout this review, the term “bimetallic catalysts” broadly refers to Cu-based systems containing a second metallic element, which may be present as a metallic alloy, an intermetallic compound, an atomically dispersed promoter species, or an oxide promoter or support component that forms Cu-M or Cu-MOx interfacial structures. Experimental findings and density functional theory calculations are integrated to clarify how second metals regulate electronic structures, interfacial sites, oxygen vacancies, and hydrogen activation, thereby governing the competition between the formate pathway and RWGS. The dynamic evolution of active sites and the concentration-dependent role of reaction-generated water are also discussed. Finally, current challenges in machine learning-assisted catalyst development are assessed, and future directions involving operando characterization, hydrophobic interface engineering, reactor-level water management, and interpretable data-driven catalyst design are proposed to guide catalyst optimization and practical implementation.

Unknown authors · Catalysts · 0 citations

Review Sep 2026

Manganese Metal‐Organic Frameworks as Versatile Catalytic Platforms for Organic Transformations

Metal‐organic frameworks (MOFs), a distinguished class of crystalline porous materials, are composed of metal ions or clusters interconnected by organic linkers. MOFs are associated with different promising properties like high surface area, tunable pore structure, and significant chemical functionality that make them an attractive class of heterogeneous catalysts. The modular nature of MOFs allows for design control over their active sites within the catalytic framework. Among transition metals, manganese (Mn) has received significant attention for several reasons, including the existence of multiple accessible oxidation states (Mn 2+ , Mn 3+ , and Mn 5+ ), high redox activity, modest toxicity, and low cost. These benefits allow Mn‐MOFs to mediate a suitable host of organic transformations, such as oxidation, condensation, and multicomponent coupling reactions, under mild, green, and sustainable catalytic conditions. The combined features of the tunable structure common in MOFs and the flexible redox behavior led to enhanced catalytic performance, stability, and reusability of Mn‐MOFs. This review describes the detailed catalytic applications and mechanistic aspects of Mn‐MOFs for sustainable organic transformations developed over the past 15 years.

Unknown authors · European Journal of Inorgani... · 0 citations

Open access Aug 2026

Metal-Oxo Cluster Composition in Metal-Organic Frameworks Controls Solar-Driven CO2 Methanation Pathways.

Although metal-organic frameworks have emerged as versatile and tunable heterogeneous photocatalysts for the hydrogenation of gaseous CO2 to CH4, the role of metal-oxo cluster composition in governing this photocatalytic process remains largely unexplored. Herein, we employ an isostructural series of monometallic MIL-100(M) frameworks (M = Cr3+, Fe3+, Sc3+, Al3+, and In3+) to systematically investigate how metal-oxo cluster composition governs solar-driven CO2 methanation within a common structural platform. MIL-100(Cr)-based solids markedly outperform their analogues, achieving highly selective CO2 conversion to CH4 as confirmed by isotopic 13CO2 labeling experiments and high integral stability, with sustained catalytic operation for 132 h over six consecutive cycles under simulated sunlight irradiation. This superior photocatalytic performance arises from the synergistic combination of chemical robustness, favorable CO2/CO chemisorption within the framework, efficient photothermal energy conversion, and enhanced photoinduced charge-carrier dynamics. Operando Fourier Transform infrared measurements reveal a CO2 methanation mechanism involving formate, mono-, and bi-dentate methoxy species as key intermediates. These findings identify metal-oxo cluster composition as a key descriptor controlling adsorption behavior, charge-carrier dynamics, photothermal response, and dominant light-driven reaction pathways in MOF photocatalysts for solar-driven CO2 methanation.

Vitor Fernandes de Almeida, Zahraa Abou Khalil, Juan José Ramírez Hernández et al. · Journal of the American Chem... · 0 citations