Boosting Catalysis of Pd Nanoparticles in MOFs by Pore Wall Engineering: The Roles of Electron Transfer and Adsorption Energy

Advanced Materials, Journal Year: 2020, Volume and Issue: 32(30)

Published: June 11, 2020

The chemical environment of metal nanoparticles (NPs) possesses significant influence on their catalytic performance yet is far from being well understood. Herein, tiny Pd NPs are encapsulated into the pore space metal-organic frameworks (MOFs), UiO-66-X (X = H, OMe, NH2 , 2OH, 2OH(Hf)), affording Pd@UiO-66-X composites. surface microenvironment readily modulated by wall engineering, via functional group and substitution in MOFs. Consequently, activity follows order Pd@UiO-66-OH > Pd@UiO-66-2OH(Hf) Pd@UiO-66-NH2 Pd@UiO-66-OMe Pd@UiO-66-H toward hydrogenation benzoic acid. It found that difference not only ascribed to distinct charge transfer between MOF, but also explained discriminated substrate adsorption energy (-OH < -2OH(Hf) -NH2 -OMe -H), based CO-diffuse reflectance infrared Fourier transform spectra density-functional theory (DFT) calculations. Pd@UiO-66-OH, featuring a high electronic state moderate energy, displays highest activity. This work highlights guest NPs, which dominated electron systematic groups host

Language: Английский

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Metal–organic frameworks as catalytic selectivity regulators for organic transformations

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

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Metal–organic frameworks (MOFs) based electrochemical biosensors for early cancer diagnosis in vitro

Coordination Chemistry Reviews, Journal Year: 2021, Volume and Issue: 439, P. 213948 - 213948

Published: April 24, 2021

Language: Английский

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An extensive review on three dimension architectural Metal-Organic Frameworks towards supercapacitor application

Journal of Power Sources, Journal Year: 2021, Volume and Issue: 488, P. 229444 - 229444

Published: Jan. 18, 2021

Language: Английский

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Metal–Organic Frameworks as Multifunctional Solid Catalysts

Trends in Chemistry, Journal Year: 2020, Volume and Issue: 2(5), P. 454 - 466

Published: March 9, 2020

Language: Английский

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Pd Supported on MIL-68(In)-Derived In₂O₃ Nanotubes as Superior Catalysts to Boost CO₂ Hydrogenation to Methanol

ACS Catalysis, Journal Year: 2020, Volume and Issue: 10(22), P. 13275 - 13289

Published: Nov. 2, 2020

Utilization of CO2 and its conversion to value-added chemicals are highly desirable alleviate the environmental concerns caused by massive anthropogenic emission. Although In2O3/Pd have been employed as efficient catalysts for hydrogenation methanol, electronic effects strong metal–support interaction (SMSI) between Pd In2O3 poorly understood, which is greatly affected morphology In2O3. Herein, we use MIL-68(In) nanorod a morphological template synthesis hollow nanotubes (h-In2O3) preparation supported methanol. Interestingly, loading on h-In2O3 showed much higher performance than with other morphologies, exhibited almost unchanged 10.5%, methanol selectively 72.4%, space-time yield 0.53 gMeOH h–1 gcat–1 over 100 h stream at 3 MPa 295 °C. After in-depth characterizations, found that different properties species can be finely tuned diverse synthetic conditions, were responsible high activity stability. The molar fraction Pd2+ in h-In2O3/Pd catalyst reached 67.6%, 3.2 times In2O3@Pd (21.3%), due surface chemistry Density function theory results indicated donated more electrons curved (222) pristine surface, was critical facilitate H2 adsorption formation oxygen vacancy. This work demonstrates controlling modify both property SMSI In2O3, origins catalytic performance.

Language: Английский

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Structure–Activity Relationships That Identify Metal–Organic Framework Catalysts for Methane Activation

ACS Catalysis, Journal Year: 2019, Volume and Issue: 9(4), P. 3576 - 3587

Published: March 8, 2019

In this work, we leverage advances in computational screening based on periodic density functional theory (DFT) to study a diverse set of experimentally derived metal–organic frameworks (MOFs) with accessible metal sites for the oxidative activation methane. We find that thermodynamic favorability forming metal-oxo active site has strong, inverse correlation reactivity toward C–H bond wide range MOFs. This scaling relationship is found hold over MOFs varying coordination environments and compositions, provided bonds framework atoms are conserved. The need conserve an important constraint correlations but also demonstrates route intentionally break generate novel catalytic reactivity. Periodic trends observed across data screened MOFs, later transition metals less stable more reactive sites. Collectively, results work provide robust rules-of-thumb choosing investigate methane at moderate reaction conditions.

Language: Английский

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An Overview of Metal–Organic Frameworks for Green Chemical Engineering

Engineering, Journal Year: 2021, Volume and Issue: 7(8), P. 1115 - 1139

Published: July 8, 2021

Given the current global energy and environmental issues resulting from fast pace of industrialization, discovery new functional materials has become increasingly imperative in order to advance science technology address associated challenges. The boom metal–organic frameworks (MOFs) MOF-derived recent years stimulated profound interest exploring their structures applications. preparation, characterization, processing MOF are basis full engagement industrial implementation. With intensive research these topics, it is time promote practical utilization MOFs on an scale, such as for green chemical engineering, by taking advantage superior functions. Many famous have already demonstrated superiority over traditional solving real-world problems. This review starts with basic concept chemistry ends a discussion production exploitation several fields. Its goal provide general scope application inspire researchers convert focus academic one After obstacles cost, scale-up processability, stability been overcome, MOF-based devices will gradually enter factory, part our daily lives, help create future based living.

Language: Английский

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Neighboring Zn–Zr Sites in a Metal–Organic Framework for CO₂ Hydrogenation

Journal of the American Chemical Society, Journal Year: 2021, Volume and Issue: 143(23), P. 8829 - 8837

Published: June 7, 2021

ZrZnOx is active in catalyzing carbon dioxide (CO2) hydrogenation to methanol (MeOH) via a synergy between ZnOx and ZrOx. Here we report the construction of Zn2+–O–Zr4+ sites metal–organic framework (MOF) reveal insights into structural requirement for MeOH production. The are obtained by postsynthetic treatment Zr6(μ3-O)4(μ3-OH)4 nodes MOF-808 ZnEt2 mild thermal remove capping ligands afford exposed metal catalysis. resultant MOF-808-Zn catalyst exhibits >99% selectivity CO2 at 250 °C high space-time yield up 190.7 mgMeOH gZn–1 h–1. catalytic activity stable least 100 h. X-ray absorption spectroscopy (XAS) analyses indicate presence centers instead ZnmOn clusters. Temperature-programmed desorption (TPD) hydrogen H/D exchange tests show activation H2 Zn2+ centers. Open Zr4+ also critical, as supported on Zr-based other MOFs without open fail produce MeOH. TPD reveals importance bicarbonate decomposition under reaction conditions generating activation. well-defined local structures metal-oxo provide unique opportunity elucidate details bifunctional

Language: Английский

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Porous materials for capture and catalytic conversion of CO2 at low concentration

Coordination Chemistry Reviews, Journal Year: 2022, Volume and Issue: 465, P. 214576 - 214576

Published: April 29, 2022

Language: Английский

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