Construction of Highly Active Pd–Ti3+ Sites in Defective Pd/TiO2 Catalysts for Efficient Hydrogenation of Styrene–Butadiene–Styrene DOI
Shidong Wang,

Bingqing Ge,

Zongxuan Yang

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(3), P. 1432 - 1442

Published: Jan. 12, 2024

Defect-rich Pd/TiO2 catalysts are intensively adopted in heterogeneous hydrogenation reactions; however, the complexity of defect structure makes it difficult to precisely identify which Pd-defect combination dominates catalytic activity. Herein, defective TiO2 nanoflakes with tunable ratios Vo Ti3+ defects were synthesized and used construct Pd–Vo Pd–Ti3+ active sites after loading Pd investigate role regulating structural properties catalysts. Combining experimental results theoretical calculations, we reveal that both act as electron donors for induce strong metal–support interaction. When compared defect, behaves more significantly donates electrons, causing species on be better dispersed rich electrons. These unique features endow centers enhanced adsorption–activation ability toward C═C H2 well reduced energy barrier rate-limiting step, thus improving intrinsic The site manifests a high turnover frequency 348 h–1 degree 97% styrene–butadiene–styrene, outperforms (254 78%) nanoparticle (217 53%). This work provides deep insight into metal sites, can guide development high-performance versatile applications.

Language: Английский

The promoting effect of H2O on rod-like MnCeOx derived from MOFs for toluene oxidation: A combined experimental and theoretical investigation DOI
Xiaodong Zhang, Fukun Bi,

Ziqiao Zhu

et al.

Applied Catalysis B Environment and Energy, Journal Year: 2021, Volume and Issue: 297, P. 120393 - 120393

Published: May 25, 2021

Language: Английский

Citations

386
Electronic Modulation Caused by Interfacial Ni‐O‐M (M=Ru, Ir, Pd) Bonding for Accelerating Hydrogen Evolution Kinetics DOI
Liming Deng, Feng Hu, Mingyue Ma

et al.

Angewandte Chemie International Edition, Journal Year: 2021, Volume and Issue: 60(41), P. 22276 - 22282

Published: Aug. 24, 2021

Abstract Designing definite metal‐support interfacial bond is an effective strategy for optimizing the intrinsic activity of noble metals, but rather challenging. Herein, a series quantum‐sized metal nanoparticles (NPs) anchored on nickel metal–organic framework nanohybrids (M@Ni‐MOF, M=Ru, Ir, Pd) are rationally developed through spontaneous redox strategy. The metal‐oxygen bonds between NPs and Ni‐MOF guarantee structural stability sufficient exposure surface active sites. More importantly, such precise feature can effectively modulate electronic structure hybrids charge transfer formed Ni‐O‐M bridge then improves reaction kinetics. As result, representative Ru@Ni‐MOF exhibits excellent hydrogen evolution (HER) at all pH values, even superior to commercial Pt/C recent noble‐metal catalysts. Theoretical calculations deepen mechanism understanding HER performance optimized adsorption free energies water due interfacial‐bond‐induced electron redistribution.

Language: Английский

Citations

268
Microenvironment Modulation in Metal–Organic Framework-Based Catalysis DOI
Long Jiao, Jingxue Wang, Hai‐Long Jiang

et al.

Accounts of Materials Research, Journal Year: 2021, Volume and Issue: 2(5), P. 327 - 339

Published: Feb. 26, 2021

ConspectusThe fine design and regulation of catalysts play critical roles in the development catalysis. The microenvironment, which gives rise to unique spatial structures electronic properties around catalytic sites, has been proven dramatically regulate behavior enzymes homogeneous However, understanding microenvironment modulation (MEM) sites remains challenging very limited heterogeneous catalysis mainly due lack structural precision and/or tailorability traditional solid catalysts. Among diverse materials, metal–organic frameworks (MOFs), a class porous crystalline solids, have intensively studied as recent years. atomically precise well tunable MOFs make them an ideal platform for rationally regulating surrounding sites. Accordingly, their well-defined hold great promise elucidating how affects resulting performance. Nevertheless, investigations accurate control over modulated are still limited. Therefore, it is importance summarize related results provide in-depth insights into MOF-based catalysis, accelerating future this emerging research topic.In Account, we presented summary our attempts optimize performance materials via modulation. In view component advantages MOFs, deliver general fundamentals rational Initially, opportunities brought about by engineering, including origin abundant active flexible strategies, structure, introduced detail. next section, focus on specific strategies dominate molecular/electron-transfer process intrinsic activity Meanwhile, chemical basis underlying structure–property relationship behind enhanced will be highlighted. Finally, major challenges outlooks further discussed. It expected that Account would afford significant inspiration toward engineering

Language: Английский

Citations

260
Programmable Logic in Metal–Organic Frameworks for Catalysis DOI
Yu Shen, Ting Pan,

Liu Wang

et al.

Advanced Materials, Journal Year: 2021, Volume and Issue: 33(46)

Published: May 28, 2021

Abstract Metal–organic frameworks (MOFs) have emerged as one of the most widely investigated materials in catalysis mainly due to their excellent component tunability, high surface area, adjustable pore size, and uniform active sites. However, overwhelming number MOF complex structures has brought difficulties for researchers select construct suitable MOF‐based catalysts. Herein, a programmable design strategy is presented based on metal ions/clusters, organic ligands, modifiers, functional materials, post‐treatment modules, which can be used components, structures, morphologies catalysts different reactions. By establishing corresponding relationship between these modules functions, accurately efficiently heterometallic MOFs, chiral conductive hierarchically porous defective composites, MOF‐derivative Further, this approach also regulate physical/chemical microenvironments pristine heterogeneous catalysis, electrocatalysis, photocatalysis. Finally, challenging issues opportunities future research are discussed. Overall, modular concept review applied potent tool exploring structure–activity relationships accelerating on‐demand multicomponent

Language: Английский

Citations

210
Metal–Organic Frameworks Enhance Biomimetic Cascade Catalysis for Biosensing DOI
Weiqing Xu, Lei Jiao, Yu Wu

et al.

Advanced Materials, Journal Year: 2021, Volume and Issue: 33(22)

Published: April 23, 2021

Abstract Multiple enzymes‐induced biological cascade catalysis guides efficient and selective substrate transformations in vivo. The biomimetic systems, as ingenious strategies for signal transduction amplification, have a wide range of applications biosensing. However, the fragile nature enzymes greatly limits their applications. In this regard, metal–organic frameworks (MOFs) with porous structures, unique nano/microenvironments, good biocompatibility been skillfully used carriers to immobilize shielding them against hash surroundings improving catalytic efficiency. For another, nanomaterials enzyme‐like properties brilliant stabilities (nanozymes), widely applied ameliorate low stability enzymes. Inheriting abovementioned merits MOFs, performances MOFs‐immboilized nanozymes could be significantly enhanced. Furthermore, addition carriers, some MOFs can also serve nanozymes, expanding systems. Herein, recent advances fabrication MOFs‐involving enzymes/nanozymes systems biosensing are highlighted. Integrating diversified output modes, including colorimetry, electrochemistry, fluorescence, chemiluminescence, surface‐enhanced Raman scattering, sensitive detection various targets (including molecules, environmental pollutants, enzyme activities, so on) realized. Finally, challenges opportunities about further constructions reaction briefly put forward.

Language: Английский

Citations

184
Metal–organic frameworks as catalytic selectivity regulators for organic transformations DOI
Jun Guo,

Yutian Qin,

Yanfei Zhu

et al.

Chemical Society Reviews, Journal Year: 2021, Volume and Issue: 50(9), P. 5366 - 5396

Published: Jan. 1, 2021

Selective organic transformations using metal–organic frameworks (MOFs) and MOF-based heterogeneous catalysts have been an intriguing but challenging research topic in both the chemistry materials communities.

Language: Английский

Citations

184
Current Progress in 2D Metal–Organic Frameworks for Electrocatalysis DOI Creative Commons
Usman Khan,

Adeela Nairan,

Junkuo Gao

et al.

Small Structures, Journal Year: 2022, Volume and Issue: 4(6)

Published: Sept. 16, 2022

The 2D nanosheets of metal–organic frameworks (MOFs) have recently emerged as a promising material that makes them valuable in widespread electrocatalytic fields due to their atomic‐level thickness, abundant active sites, and large surface area. Efficient electrocatalysts for hydrogen evolution reaction (HER), oxygen (OER), overall water splitting are highly desired with low overpotentials promote the industrial applications energy conversion devices. MOF nanostructures provide long‐term stability high electrical conductivity enhance catalyst activity durability. This review briefly summarizes synthesis HER/OER/water splitting. More attention is focused on synthetic strategies derivatives. catalytic performance superior properties these materials highlighted. outperformance originates from rational design, myriad thickness. current future challenges this field scientific perspectives overcome It suggested construction can develop state‐of‐the‐art electrocatalyst environmental division.

Language: Английский

Citations

175
Cucurbiturils‐Mediated Noble Metal Nanoparticles for Applications in Sensing, SERS, Theranostics, and Catalysis DOI
Lili Tan, Mengying Wei, Shang Li

et al.

Advanced Functional Materials, Journal Year: 2020, Volume and Issue: 31(1)

Published: Sept. 28, 2020

Abstract Noble metal nanoparticles (NMNPs), which spring up like mushrooms, are gaining momentum owing to their unique physicochemical characteristics. Cucurbiturils, a class of synthetic macrocycles with intriguing and peculiar host–guest properties, have stimulated tremendous research interest in recent years. The marriage NMNPs cucurbiturils is expected integrate enhance the excellent characteristics both components, e.g., precisely controlled particle size, stability, assembly, surface functionality, biocompatibility, tunable optical high catalytic activities. This review systematically outlines progress on fabricating strategies important applications cucurbiturils‐mediated sensing, surface‐enhanced Raman scattering, theranostics, catalysis. A brief outlook future development also presented.

Language: Английский

Citations

139
Surface-Clean Au25 Nanoclusters in Modulated Microenvironment Enabled by Metal–Organic Frameworks for Enhanced Catalysis DOI
He Wang, Xiyuan Liu, Weijie Yang

et al.

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(48), P. 22008 - 22017

Published: Nov. 21, 2022

Metal nanoclusters (NCs) with atomically precise structures have sparked interest in catalysis. Unfortunately, their high aggregation tendency and the spatial resistance of surface ligands pose significant challenges. Herein, Au25 NCs are encapsulated into isoreticular metal-organic frameworks (MOFs), namely UiO-66-X (X = H, NH2, OH, NO2), followed by removal on NCs. The resulting surface-clean NCs, protected MOF confinement, exhibit much superior activity stability respect to pristine oxidative esterification furfural. Remarkably, experimental theoretical results jointly demonstrate that diverse functional groups modulate electronic state, giving rise discriminated substrate adsorption energy Au25@UiO-66-X. As a result, electron density suitable ability dominate trend: Au25@UiO-66-NH2 > Au25@UiO-66-OH Au25@UiO-66 Au25@UiO-66-NO2. This work develops new strategy for stabilization metal pore wall-engineered MOFs enhanced

Language: Английский

Citations

120
Recent Advances in Catalytic Confinement Effect within Micro/Meso‐Porous Crystalline Materials DOI
Jingjing Dai, Hongbo Zhang

Small, Journal Year: 2021, Volume and Issue: 17(22)

Published: March 16, 2021

Abstract Micro/meso‐porous crystalline materials with a well‐defined pore structure, such as zeolites, carbon nanotubes, and metal–organic frameworks, are of great significance in the development catalytic systems for scientific industrial demands. The confinement effect aroused by features porous has triggered interest heterogeneous catalysis. Catalytic reactions confined spaces exhibit unique behaviors compared to those observed on bulk materials. More interestingly, chemical reactivity can be modulated different ways effect, despite fact that mechanism how changes reaction remains unclear. In this review, systematic discussion fundamental understanding is provided concerning concept highlighting impact effects diffusion, adsorption/desorption, typical micro/meso‐porous materials, including frameworks. Relevant studies demonstrate affords not only shape selectivity against reactants/products, but also modulates surface electron distribution active species within environments, thereby successively affecting reactivity, selectivity, stability. This review provides useful guide researchers attempting design excellent catalysts based

Language: Английский

Citations

118