Recent Advances on Heterogeneous Non-noble Metal Catalysts toward Selective Hydrogenation Reactions

ACS Catalysis, Год журнала: 2023, Номер 13(13), С. 8902 - 8924

Опубликована: Июнь 21, 2023

Selective hydrogenation reactions provide a pivotal and promising strategy for upgrading substances with unsaturated functional groups, in which supported non-noble metal catalysts play crucial role determining catalytic performance toward desirable products. By means of precipitation method, hydrothermal solvothermal methods, sol–gel synthesis as well ion exchange various kinds high efficiency have been reasonably designed developed. The detailed investigations by virtue comprehensive studies demonstrated that addition to the inherent properties elements, nanosized effect, metal-alloy metal–support interaction impose significant influences on resulting behavior. Moreover, we discuss applications heterogeneous focus aldehydes/ketones, alkynes alkadienes, functionalized nitroaromatic hydrocarbons. In this review, basis achievements representative investigations, suggestions prospects further progresses development selective put forward.

Язык: Английский

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Nanoarchitectonics of Non-Noble-Metal-Based Heterogeneous Catalysts for Transfer Hydrogenation Reactions: Detailed Insights on Different Hydrogen Sources

ACS Catalysis, Год журнала: 2024, Номер 14(6), С. 4211 - 4248

Опубликована: Март 5, 2024

Catalytic transfer hydrogenation (CTH) methodology has drawn profound attention of researchers as an economical and environmentally benign alternate to conventional method. Unlike method, CTH exhibits better reaction efficiency atom economy, it makes use simple, easily accessible, low-cost hydrogen sources. Current research on reactions is oriented toward the development non-noble-metal-based catalysts due their high abundance potential large-scale applicability. In this Review, different organic transformation reactions, such nitroarenes, nitriles, alkenes, alkynes, carbonyl compounds, hydrogenolysis, reductive amination, formylation using sources have been summarized comprehensively. addition, synthesis strategies heterogeneous structure–activity relationship involving metal–support interaction, single-atom catalysis, synergistic effect are highlighted. Furthermore, optimization parameters─such temperature, time, solvents, additives─for enhancing catalytic activity selectivity product discussed in detail. This Review provides detailed insights into recent progress made with a specific focus catalyst development, sources, mechanistic exploration.

Язык: Английский

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Recent Advances in Reversible Liquid Organic Hydrogen Carrier Systems: From Hydrogen Carriers to Catalysts

Advanced Materials, Год журнала: 2024, Номер 36(37)

Опубликована: Фев. 20, 2024

Abstract Liquid organic hydrogen carriers (LOHCs) have gained significant attention for large‐scale storage due to their remarkable gravimetric capacity (HSC) and compatibility with existing oil gas transportation networks long‐distance transport. However, the practical application of reversible LOHC systems has been constrained by intrinsic thermodynamic properties performances associated catalysts in (de)hydrogenation cycles. To overcome these challenges, thermodynamically favored carriers, high‐performance catalysts, catalytic procedures need be developed. Here, advances recent years summarized, primarily centered on regular catalyzed homogeneous heterogeneous including dehydrogenative aromatization cycloalkanes arenes N ‐heterocyclics ‐heteroarenes, as well reverse hydrogenation processes. Furthermore, development metal complexes coupling, a new family based alcohols is described that can release H 2 under relatively mild conditions. Finally, views next steps challenges field technology are provided, emphasizing resources low‐cost technologies, scenarios.

Язык: Английский

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Value‐Added Upcycling of PET to 1,4‐Cyclohexanedimethanol by a Hydrogenation/Hydrogenolysis Relay Catalysis

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(37)

Опубликована: Июнь 26, 2024

Abstract We present an innovative process for directly transforming poly(ethylene terephthalate) (PET), a polymer extensively used in food and beverage packaging, into trans ‐isomer‐enriched 1,4‐cyclohexanedimethanol (CHDM), key ingredient advanced specialty polymers. Our approach leverages dual‐catalyst system featuring palladium on reduced graphene oxide (Pd/ r ‐GO) oxalate‐gel‐derived copper‐zinc ( og ‐CuZn), utilizing hydrogenation/hydrogenolysis relay catalysis. This method efficiently transforms PET polyethylene‐1,4‐cyclohexanedicarboxylate (PECHD), which is then converted CHDM with impressive overall yield of 95 % two‐stage process. effectively handles various post‐consumer plastics, converting them yields between 78 89 across different substrates. Additionally, we demonstrate the applicability scalability this through temperature‐programmed three‐stage 10‐gram scale, results purified isolated 87 notably higher / cis ratio up to 4.09/1, far exceeding that commercially available CHDM. research not only provides viable route repurposing waste but also enhances control selectivity patterns multistage

Язык: Английский

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Oxygen-Vacancy-Induced Built-In Electric Field across MoCo Dual-Atomic Site Catalyst for Promoting Hydrogen Spillover in Hydrocracking and Hydrodesulfurization

ACS Catalysis, Год журнала: 2024, Номер 14(5), С. 3208 - 3217

Опубликована: Фев. 15, 2024

The design and construction of highly efficient catalytic active sites for promoting hydrogen spillover are great significance improving hydrocracking (HCK) hydrodesulfurization (HDS) performance in slurry-phase hydrogenation vacuum residue (VR) but still challenging. Herein, we report a carbon-supported MoCo dual-atomic site catalyst (MoCo DAC/C) propose an oxygen-vacancy-induced built-in electric field (BIEF) regulation mechanism HCK HDS. It was found that the coordination structure reconstructed formed O vacancies situ during process. formation not only provided macromolecular adsorption also broke electronic balance weak BIEF between Mo Co atoms. Meanwhile, H2 activated at to form species. promoted from by Mo–C–Co bridging bond, thus greatly. In VR, DAC/C demonstrates remarkable activity with TOFT calculated total metals up 0.77 s–1 (two times enhancement than single atoms (SAs)/C), per pass conversion VR 76 wt %, liquid product yield 92 coke content 0.55 %. shows robust HDS dibenzothiophene (DBT) 70 Density functional theory reveals leads discrepancy Bader charge atoms, resulting local can favor diffusion positively charged (+0.10 e−) H atom. This work proposes atomic scale enhancing reaction process spillover, which novel insights development high-performance catalysts.

Язык: Английский

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Flatland of Graphene's derivatives: Classification, synthesis, mechanisms, role of defects, applications, and prospectives

Coordination Chemistry Reviews, Год журнала: 2025, Номер 528, С. 216421 - 216421

Опубликована: Янв. 8, 2025

Язык: Английский

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High Performance Polyoxometalate-Stabilizing Pt Nanocatalysts for Quinoline Hydrogenation with Water-Mediated Dynamic Hydrogen

ACS Catalysis, Год журнала: 2024, Номер 14(7), С. 5344 - 5355

Опубликована: Март 26, 2024

In this work, a Keggin-type platinum substituted polyoxometalate (POM) is constructed by the reaction of monolacunary phosphotungstate precursor [PW11O39]7– with chloroplatinic acid. The as-obtained tetrabutylammonium salt (TBA-PWPt) demonstrates that dimeric Pt2+ ions are incorporated into POM frameworks and linked two anions. Notably, once Pt-substituted anion reduced H2, anion-stabilizing Pt nanocatalysts generated, which greatly facilitates forming oxygen vacancies adjacent to Pt0 species. show superior catalytic activity stability for selective hydrogenation quinoline 1,2,3,4-tetrahydroquinoline in water. Detailed investigations elucidate stronger adsorption on surface H2 activated at POMs-Pt interface site. Moreover, density functional theory (DFT) calculations H2O adsorbed interfacial then undergoes homolytic dissociation produce hydroxyl group (OH–) hydride (H–) H– species transferred N-containing pyridine ring hydrogenation, OH– help promote heterolytic H+ Sequentially, produced proton groups generate H2O, cycle completed.

Язык: Английский

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Heterogeneous Iridium-Catalyzed Carbene N–H Bond Insertion with α-Alkyl Diazo Esters

ACS Catalysis, Год журнала: 2024, Номер 14(7), С. 4690 - 4698

Опубликована: Март 13, 2024

A heterogeneous iridium single-atom site catalyst (Ir-SA) was synthesized and investigated in catalyzing the carbene insertion reaction with challenging α-alkyl diazo ester substrates. With only 0.23 mol % loading, our Ir-SA demonstrated remarkable performance N–H bond reactions involving various (hetero) aryl amines coupled esters. Notably, case of using a chiral diamino substrate two reactive sites, exhibited high selectivity toward single insertion, leading to generation class unsymmetric ligands. Further mechanism study revealed that lower activation barrier associated step, as compared either β-hydride elimination or downstream dual accounted for observed this catalyzed by Ir-SA.

Язык: Английский

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Selective electro-reduction of CO2 into methane and formic acid using efficient bimetallic and bimetallic oxide electrocatalysts in liquid-fed electrolyzers

Journal of Power Sources, Год журнала: 2025, Номер 633, С. 236393 - 236393

Опубликована: Фев. 11, 2025

Язык: Английский

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The Role of Mo Single Atoms and Clusters in Enhancing Pt Catalyst for Benzene Hydrogenation: Distinguishing Between Benzene Spillover and Electronic Effect

ACS Catalysis, Год журнала: 2024, Номер 14(7), С. 5016 - 5026

Опубликована: Март 19, 2024

Reactant spillover and electronic effects are two indistinguishable factors that influence MoO3 promoters in benzene hydrogenation on Pt-MoO3 catalysts. Previous studies have primarily focused the significance of hydrogen while neglecting transfer effect originating from MoO3. Herein, we synthesized Pt/CNT, Pt–Mo1/CNT with Mo single atoms, Pt–Mocluster/CNT MoOx cluster by using atomic layer deposition. The catalyst exhibited higher activity (3361.8 h–1) at 50 °C, which was twice as high Pt/CNT. In contrast, presence closely interacting clusters Pt nanoparticles inhibited catalyst. Kinetic experiments, DFT calculations, situ FTIR, AIMD simulations revealed atoms multiwalled carbon nanotubes did not alter structure or state but enhanced their increasing coverage via spillover. On other hand, although increased promoters, changes resulted a energy barrier for rate-determining step.

Язык: Английский

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