Selectivity control by zeolites during methanol-mediated CO₂ hydrogenation processes

Chemical Society Reviews, Год журнала: 2025, Номер unknown

Опубликована: Янв. 1, 2025

The thermocatalytic conversion of CO2 with green or blue hydrogen into valuable energy and commodity chemicals such as alcohols, olefins, aromatics emerges one the most promising strategies for mitigating global warming concerns in future. This process can follow either a CO2-modified Fischer-Tropsch synthesis route methanol-mediated route, latter being favored its high product selectivity beyond Anderson-Schulz-Flory distribution. Despite progress CO2-led over bifunctional metal/zeolite catalysts, challenges persist developing catalysts both activity due to complexity hydrogenation reaction networks difficulty controlling C-O bond activation C-C coupling on multiple active sites within zeolites. Moreover, different construction proximity modes bifunctionality involving redox-based metallic acidic zeolite have been explored, which not systematically reviewed derive reliable structure-reactivity relationships. To bridge this "knowledge gap", review, we will provide comprehensive critical overview contemporary research zeolite-confined metal alcohol zeolite-based tandem/cascade catalytic systems C2+ hydrocarbons via route. Accordingly, special emphasis be placed evaluating how confinement effects "redox-acid" influence outcomes, particularly regarding selectivity, has also analyzed from mechanistic standpoint. review examine synergistic interactions among various catalyst components that govern catalysis, offering insights rational design new improved systems. By discussing current recognizing future opportunities using aims contribute advancement sustainable efficient processes valorization.

Язык: Английский

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Rational Design of Catalysts with Spinel Nanostructures for Thermal-Driven C1 Conversion

ACS Catalysis, Год журнала: 2024, Номер 14(13), С. 9812 - 9828

Опубликована: Июнь 17, 2024

The oriented conversion of C1 molecules including CO, CO2, CH4, and CH3OH has received great attention in the past few decades because its essential role sustainable chemistry. Spinel oxides with fine hardness, thermal stability, tunable chemical properties are advantageous catalysts or precursors activation inert for production high-value-added chemicals. This review provides a thorough overview recent developments spinel-structured nanocatalysts processes thermal-driven conversion, highlighting advantages deriving active metals, stabilizing metal cations, constructing adjacent synergic sites, tuning oxygen vacancies. Finally, potential challenges development directions discussed application reactions.

Язык: Английский

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Construction of Highly Active Fe₅C₂–FeCo Interfacial Sites for Oriented Synthesis of Light Olefins from CO₂ Hydrogenation

ACS Catalysis, Год журнала: 2025, Номер unknown, С. 1112 - 1122

Опубликована: Янв. 3, 2025

The hydrogenation of CO2 into high-value chemistry is seen as one the viable strategies for solving energy crisis future. Light olefins have attracted considerable attention basic feedstocks in industry. In this work, a series Fe–Co bimetallic active site catalysts were constructed by typical sol–gel strategy. synergistic regulation layout catalyst highly interfaces and exhibited high conversion (56.9%) CO2, low CO selectivity (3.6%), (40.5%) light olefins, remarkable yield (22.2%). results associated characterization analysis indicate that activity formed sites are fundamental reason olefins. introduction cobalt drive RWGS reaction forward (Le Chatelier's Principle), which further enhances conversion. addition, dynamic evolution physical phase structure, elemental composition valence, H2 adsorption ability, formation process during analyzed situ DRIFT spectra other characterizations, potential mechanism to proposed. This work provides an effective rational design strategy bimetals with promote efficient oriented synthesis

Язык: Английский

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Split Syntheses: Introducing Bottom-Up Control over Aluminum in SSZ-13 and ZSM-5 Zeolites

JACS Au, Год журнала: 2025, Номер unknown

Опубликована: Янв. 28, 2025

Zeolite synthesis is known as a difficult-to-control process, with many degrees of freedom that have partially uncharted impact on the final product. Due to this, zeolite scientists regarded initial mixing (aging) stage only time at which chemical composition mixture can be impacted without heavily disrupting delicate equilibria are play during crystallization. Recently, however, this view has started change, innovative techniques such charge density mismatch or electro-assisted showing addition new elements reactor midsynthesis might lead and surprising outcomes. In manuscript, we show by intermittent removal certain fractions, notably Al-rich solids Si-rich liquids, from reaction medium an interzeolite conversion FAU-to-CHA (and FAU-to-MFI), one control Si/Al ratio product, impacting time, particle size, divalent cation capacity This approach was named "split synthesis" led several insights. By removing some liquid phase after 40 min synthesis, daughter lowered value 20 (starting 40), while capacity, performance indicator for acid metal-catalyzed reactions, kept maximized. On other hand, when were removed in cases colloidal silica supplemented), able rapidly synthesize small SSZ-13 zeolites ratios up 180. These high-Si had sizes range 100–150 nm traditionally difficult crystallize hydroxide medium. They showed great olefin yield (6%) CO2 H2 ZnZrOx cocatalyst.

Язык: Английский

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Electrocatalytic Hydrogenation Boosted by Surface Hydroxyls‐Modulated Hydrogen Migration over Nonreducible Oxides

Advanced Materials, Год журнала: 2025, Номер unknown

Опубликована: Фев. 17, 2025

Abstract The migration of atomic hydrogen species over heterogeneous catalysts is deemed essential for hydrogenation reactions, a process closely related to the catalyst's functionalities. While surface hydroxyls‐assisted spillover well documented on reducible oxide supports, its effect widely‐used nonreducible especially in electrocatalytic reactions with water as source, remains subject debate. Herein, oxide‐anchored copper single‐atom catalyst (Cu 1 /SiO 2 ) designed and uncover that hydroxyls SiO can serve efficient transport channels spillover, thereby enhancing activated coverage favoring reaction. Using dechlorination model reaction, Cu delivers hydrodechlorination activity 42 times greater than commercial Pd/C. An integrated experimental theoretical investigation elucidates facilitate intermediates formed at sites, boosting active . This work demonstrates feasibility acting hydrogen‐species boost supports paves way designing advanced selective electrocatalysts.

Язык: Английский

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Advances in integrated catalysts for CO2 thermal hydrogenation to multicarbon products

Chem Catalysis, Год журнала: 2025, Номер unknown, С. 101264 - 101264

Опубликована: Фев. 1, 2025

Язык: Английский

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Construction of robust Ni-based catalysts for low-temperature Sabatier reaction

Chemical Communications, Год журнала: 2024, Номер 60(81), С. 11466 - 11482

Опубликована: Янв. 1, 2024

The construction of robust Ni-based catalysts for low-temperature Sabatier reaction has been reviewed in detail. perspectives on this topic have also provided future catalyst design.

Язык: Английский

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CO ₂ hydrogenation to light olefins: Four matching rules for constructing high-performance bifunctional MCs-zeolites-based catalysts

Catalysis Reviews, Год журнала: 2024, Номер unknown, С. 1 - 76

Опубликована: Окт. 9, 2024

CO2 hydrogenation with renewable H2 to produce the chemicals, particularly light olefins, is a feasible approach mitigate emissions and realize carbon resources recycling. The coupling of "CO2-to-methanol catalysts (MCs)" "methanol-to-light olefins zeolites" can directly effectively convert into but constructing efficient bifunctional MCs-Zeolites still huge challenge owing complex structure-property relationships for single catalytic component as well suitable assembling these two components. In this review, we summarize four matching rules containing in catalysts: Rule I screens out qualified MCs achieve high methanol selectivity at temperatures; II zeolites efficiently catalyze olefins; further, III proposes efficiency-matching between "MCs formation" "Zeolites conversion olefins" increase CO2-to-light efficiency; IV optimization spatial distributions Zeolites improve light-olefins yield. cross-fertilization has innovatively constructed membrane-controlled bi-components sandwich catalysts. This review further provided ideas design more-advanced future.

Язык: Английский

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Advanced Zeolite‐based Catalysts for CO2 Hydrogenation to Targeted High‐Value Chemicals and Fuels

Chemistry - An Asian Journal, Год журнала: 2025, Номер unknown

Опубликована: Янв. 31, 2025

The excessive use of fossil fuels has resulted in elevated CO2 emissions the atmosphere, significantly impacting climate and global environment. catalytic conversion into high-value chemicals been recognized as a promising strategy to mitigate emissions. Light olefins, aromatics, alcohols, etc. are widely used chemical synthesis intermediates. To enhance efficiency selectivity for producing these chemicals, various catalysts have developed. Among them, zeolite-based garnered significant attention due their unique microporous structure, shape-selective catalysis capability, high thermal stability, tunable acidity. This article focuses on distinctive structural characteristics zeolites notable representative applications, with particular emphasis impact zeolite properties performance reaction mechanism. Additionally, we discuss current challenges fabricating highly efficient future development prospects improving industrial-scale applications. We propose rational strategic insights pave way utilization CO₂ valuable resource.

Язык: Английский

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Catalytic Properties of ZnZrOx Obtained via Metal–Organic Framework Precursors for CO2 Hydrogenation to Prepare Light Olefins

Metals, Год журнала: 2025, Номер 15(4), С. 380 - 380

Опубликована: Март 28, 2025

The conversion of CO2 into light olefins over bifunctional catalysts is a promising route for producing high-value-added products. This approach not only mitigates excessive emissions but also reduces the chemical industry’s reliance on fossil fuels. Among catalysts, ZnZrOx widely used due to its favorable oxide composition. In this work, solid solution was synthesized by calcining an MOF precursor, resulting in large specific surface area and small particle size. Characterization studies revealed that prepared via calcination exhibited enhanced activation H2 dissociation capacity compared using co-precipitation method. situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) showed adsorption led formation carbonate species, while HCOO* CH3O* intermediates were generated upon exposure reaction gas. When combined with SAPO-34 molecular sieves under conditions 380 °C, 3 MPa, 6000 mL·g_cat−1·h−1, reached 34.37%, olefin yield 15.13%, demonstrating superior catalytic performance

Язык: Английский

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