The Enigma of Methanol Synthesis by Cu/ZnO/Al₂O₃-Based Catalysts

Chemical Reviews, Год журнала: 2024, Номер 124(8), С. 4543 - 4678

Опубликована: Апрель 2, 2024

The activity and durability of the Cu/ZnO/Al

Язык: Английский

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Hydrogenation of CO ₂ for sustainable fuel and chemical production

Science, Год журнала: 2025, Номер 387(6737)

Опубликована: Фев. 27, 2025

Catalytic carbon dioxide (CO2) hydrogenation is a potential route for producing sustainable fuels and chemicals, but existing catalysts need improvement. In particular, identifying active sites understanding the interaction between components dynamic behavior of participant species remain unclear. This fundamental knowledge essential design more efficient stable catalysts. Because nature site (metal, oxide, carbide) main factor that determines catalytic activity catalysts, this Review focuses on various types heterogeneous have been recently reported in literature as CO2 conversion to C1 [carbon monoxide (CO), methanol (CH3OH), methane (CH4)], higher hydrocarbons. We focus establishing key connections active-site structures selectivity, regardless catalyst composition.

Язык: Английский

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A New Look at Catalyst Surfaces at Work: Introducing Mixed Isotope Operando Infrared Spectroscopy (MIOIRS)

ACS Catalysis, Год журнала: 2025, Номер unknown, С. 1363 - 1386

Опубликована: Янв. 8, 2025

This Perspective focuses on the characterization of supported metal catalysts by operando and CO infrared (IR) spectroscopy. IR spectroscopy is a powerful technique for probing catalyst surfaces used to identify single-atom catalysts, estimate surface availability gas phase, measure Lewis acidity. However, interpretation spectra not trivial influenced dipole–dipole interactions among molecules at medium high coverage. Such phenomenon results in spectral distortions, such as intensity transfer bands, appearance spurious shifts band position. Dipole–dipole were widely investigated understood from 1950s 1990s, but implications have been seemingly overlooked literature, with few exceptions. Inspired seminal studies field, I propose here use mixed isotopic streams, diluted 13CO 12CO, reduce dipole coupling effects retrieve more information reactions involving CO, oxidation or hydrogenation reactions. Similarly, 13CO2/12CO2 streams may be applied CO2 hydrogenation, where adsorbed commonly observed. The proposed name Mixed Isotope Operando Spectroscopy, MIOIRS. In this Perspective, will first summarize nature layers their spectra. Then, briefly describe how mixtures can partially break adsorbates distortion. both sections, give showcases vibrational heterogeneous catalysts. Finally, discuss possible MIOIRS detection quantification defect sites nanoparticles, bimetallic nanoparticles surfaces, kinetics intermediates different active sites. Notably, expanded other which strong permanent dipoles, self-catalytic reduction NOx abatement.

Язык: Английский

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Acidity drives selectivity: tuning reaction pathways of (Pt,Fe)-supported catalysts under hydrodeoxygenation conditions

Applied Catalysis B Environment and Energy, Год журнала: 2025, Номер unknown, С. 125316 - 125316

Опубликована: Март 1, 2025

Язык: Английский

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Reaction Mechanisms and Applications of Single Atom Catalysts for Thermal-Catalytic Carbon Dioxide Hydrogenation Toward Oxygenates

ACS Catalysis, Год журнала: 2024, Номер 14(21), С. 16434 - 16458

Опубликована: Окт. 23, 2024

Thermo-catalytic CO2 hydrogenation to high-value oxygenates has been regarded as one of the most powerful strategies that can potentially alleviate excessive emissions. However, due high chemical stability and variability pathways, it is still challenging achieve highly active selective hydrogenation. Single atom catalysts (SACs) with ultrahigh metal utilization efficiency extraordinary electronic features have displayed growing importance for thermo-catalytic multiple developed improve performances. Here, we review breakthroughs in developing SACs efficient toward common (CO, HCOOH, CH3OH, CH3CH2OH) following order: first, an analysis reaction mechanisms thermodynamics challenges reactions; second, a summary SAs designed by dividing them into two categories single- dual-sites; third, discussion support effects focus on approaches regulating strong metal–support interaction (MSI). Summarily, current future perspectives develop higher-performance are presented. We expect this bring more design inspiration trigger innovation catalytic evolution materials eventually benefit achievement carbon-neutrality goal.

Язык: Английский

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Mechanistic and kinetic relevance of hydrogen and water in CO2 hydrogenation on Cu-based catalysts

Journal of Catalysis, Год журнала: 2025, Номер unknown, С. 115936 - 115936

Опубликована: Янв. 1, 2025

Язык: Английский

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Enhanced CO2 hydrogenation to methanol over Cu-ZnO-Al2O3 catalyst modified with zirconium: Experimental and theoretical insights

Chemical Engineering Journal, Год журнала: 2025, Номер unknown, С. 162221 - 162221

Опубликована: Апрель 1, 2025

Язык: Английский

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Design Principles of Catalytic Materials for CO₂ Hydrogenation to Methanol

Advanced Materials, Год журнала: 2024, Номер unknown

Опубликована: Сен. 19, 2024

Abstract Heterogeneous catalysts are essential for thermocatalytic CO 2 hydrogenation to methanol, a key route sustainable production of this vital platform chemical and energy carrier. The primary catalyst families studied include copper‐based, indium oxide‐based, mixed zinc–zirconium oxides‐based materials. Despite significant progress in their design, research is often compartmentalized, lacking holistic overview needed surpass current performance limits. This perspective introduces generalized design principles catalytic materials ‐to‐methanol conversion, illustrating how complex architectures with improved functionality can be assembled from simple components (e.g., active phases, supports, promoters). After reviewing basic concepts ‐based methanol synthesis, engineering explored, building complexity single binary ternary systems. As nanostructures strongly depend on reaction environment, recent operando characterization techniques machine learning approaches examined. Finally, common rules centered around symbiotic interfaces integrating acid–base redox functions role optimization identified, pinpointing important future directions methanol.

Язык: Английский

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Exploring catalyst developments in heterogeneous CO2 hydrogenation to methanol and ethanol: A journey through reaction pathways

Journal of Energy Chemistry, Год журнала: 2024, Номер 101, С. 345 - 384

Опубликована: Окт. 10, 2024

Язык: Английский

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Gallium: A Universal Promoter Switching CO₂ Methanation Catalysts to Produce Methanol

JACS Au, Год журнала: 2024, Номер unknown

Опубликована: Дек. 20, 2024

Hydrogenation of CO2 to methanol is foreseen as a key step close the carbon cycle. In this study, we show that introducing Ga into silica-supported nanoparticles based on group 8-9 transition noble metals (M = Ru, Os, Rh, and Ir - MGa@SiO2) switches their reactivity from producing mostly methane (sel. > 97%) (>50% CH3OH/DME sel.) alongside CO only byproduct. These catalysts, prepared via surface organometallic chemistry (SOMC) approach, consist small, alloyed, narrowly distributed MGa nanoparticles, evidenced by X-ray absorption spectroscopy (XAS) adsorption studies. Notably, detailed in situ XAS diffuse reflectance Fourier transform infrared (DRIFTS) studies complemented with density functional theory (DFT) calculations indicate generates stable bulk alloys. The alloys persist during hydrogenation according XAS, resulting suppressed methanation. Meanwhile, small fraction GaO x thereby MGa-GaO interfaces are formed, IR spectroscopy, likely responsible for stabilizing methoxy intermediates favoring formation.

Язык: Английский

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