Aligning Metal Coordination Sites in Metal-Organic Framework- Enabled Metallaphotoredox Catalysis

Article Nanoscience & Nanotechnology

The Fabrication of Pd Single Atoms/Clusters on COF Layers as Co-catalysts for Photocatalytic H2 Evolution

Xiaomin Ren et al.

Summary: The optimization of the particle size of co-catalysts is crucial for enhancing the photocatalytic activity of semiconductors.

ACS APPLIED MATERIALS & INTERFACES (2022)

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Article Nanoscience & Nanotechnology

Porphyrin Coordination Polymer with Dual Photocatalytic Sites for Efficient Carbon Dioxide Reduction

Xu Ding et al.

Summary: This study presents a new system for the photocatalysis of CO2RR by incorporating dual catalytic sites into a porous coordination polymer. The system utilizes a functional ligand, TTPP, to assemble divalent nickel ions into the coordination polymer and creates samples with different molar ratios of catalytic subunits. The photocatalytic activities of these coordination polymers were evaluated and two samples, TTPP-Ni-3 and TTPP-Ni-4, displayed extraordinary performance with high CO generation rate and selectivity. The mechanism of the dual active sites was explained through theoretical simulations.

ACS APPLIED MATERIALS & INTERFACES (2022)

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Article Multidisciplinary Sciences

Visible light-driven efficient palladium catalyst turnover in oxidative transformations within confined frameworks

Jiawei Li et al.

Summary: This article introduces a new strategy to address the reoxidation problem of Pd(II) catalyst by combining photocatalyst and Pd(II) catalyst into a metal-organic framework. The results demonstrate that this method can increase the turnover number of Pd catalyst and improve the efficiency of catalytic reactions by regulating the aggregation and reoxidation processes.

NATURE COMMUNICATIONS (2022)

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Article Chemistry, Multidisciplinary

Amphiphilic Polycarbonate Micellar Rhenium Catalysts for Efficient Photocatalytic CO2 Reduction in Aqueous Media

Fang-Yu Ren et al.

Summary: A triblock amphiphilic polymer derived from the copolymerization of CO2 and epoxides is able to efficiently catalyze the visible-light-driven reduction of CO2 to CO. The polymer forms spherical micelles in water, where the metal catalyst is sequestered. The amphiphilic polycarbonate micelle rhenium catalyst shows enhanced catalytic activity and selectivity compared to the corresponding molecular rhenium catalyst in organic solvent, while also suppressing the generation of H-2.

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION (2022)

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Article Chemistry, Multidisciplinary

An Integrated Carbon Nitride-Nickel Photocatalyst for the Amination of Aryl Halides Using Sodium Azide

Arjun Vijeta et al.

Summary: In this study, a photocatalytic protocol for the selective synthesis of primary anilines was developed using a heterogeneous photocatalyst powder consisting of nickel(II) deposited on mesoporous carbon nitride. The method showed high functional group tolerance, mild reaction conditions, and easy recovery and reuse of the photocatalyst powder.

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION (2022)

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Article Chemistry, Multidisciplinary

Dual Metalation in a Two-Dimensional Covalent Organic Framework for Photocatalytic C-N Cross-Coupling Reactions

Ayan Jati et al.

Summary: This study presents a dual metalation strategy using a COF TpBpy for C-N cross-coupling reactions. The strategy demonstrates controlled metalation, recyclability, and visible-light-mediated catalysis. Experimental and theoretical studies provide insights into the catalyst and reaction mechanism.

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2022)

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Article Multidisciplinary Sciences

Deciphering the mechanism of the Ni-photocatalyzed C-O cross-coupling reaction using a tridentate pyridinophane ligand

Hanah Na et al.

Summary: This study reports a class of tridentate ligands for in-depth mechanistic study of photocatalytic C-O coupling reactions. Direct evidence for the involvement of paramagnetic Ni species in key steps of the catalytic cycle is provided, and suggests that (R)N3 ligands are a practical platform for mechanistic studies and development of new catalytic applications in nickel-catalyzed reactions.

NATURE COMMUNICATIONS (2022)

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Article Chemistry, Physical

Accelerated Direct Hydroxylation of Aryl Chlorides with Water to Phenols via the Proximity Effect in a Heterogeneous Metallaphotocatalyst

Kaixuan Wang et al.

Summary: In this study, a heterogeneous metallaphotocatalyst embedded with Ni(II) species in a photosensitive COF was reported. The concerted action of electrons, holes, and Ni species led to a significant enhancement in the activation of aryl chlorides with water. The catalyst showed 50-fold higher activity compared to its homogeneous counterpart and efficiently activated various aryl chlorides to phenols.

ACS CATALYSIS (2022)

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Article Nanoscience & Nanotechnology

Light-Induced Structural Dynamic Evolution of Pt Single Atoms for Highly Efficient Photocatalytic CO2 Reduction

Jiaxuan Fan et al.

Summary: This study investigates the structural evolution of Pt single atoms (SAs) and their impact on catalytic performance under light conditions. It reveals that Pt SAs can form different species at different light intensities, leading to different product distributions in the photocatalytic CO2 reduction process.

ACS APPLIED MATERIALS & INTERFACES (2022)

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Article Chemistry, Multidisciplinary

Transfer Hydrogenation with a Carbon-Nitride-Supported Palladium Single-Atom Photocatalyst and Water as a Proton Source

En Zhao et al.

Summary: Solar-driven transfer hydrogenation of unsaturated bonds using water as the hydrogen source is challenging due to the high barrier associated with splitting water molecules. In this study, a carbon-nitride-supported palladium single-atom heterogeneous catalyst was developed and showed unparalleled performance in photocatalytic water-donating transfer hydrogenation compared to its nanoparticle counterparts. The direct hydrogenation mechanism using in situ-generated protons from water splitting under visible-light irradiation was confirmed.

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION (2022)

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Article Chemistry, Multidisciplinary

In Situ Observation of Hot Carrier Transfer at Plasmonic Au/Metal-Organic Frameworks (MOFs) Interfaces

Shuobo Wang et al.

Summary: Constructing heterostructures on plasmonic photocatalysts can enhance charge separation, but the mechanism of interface charge transfer is not well understood. In this study, plasmonic Au and metal-organic frameworks (MOFs) heterostructures were fabricated and the charge transfer mechanism was explored. It was found that hot electrons could transfer across the Au/MOF interface and be captured by the MOF structure, while hot holes tended to transfer to and be trapped at the organic ligand. The spatially separated electrons and holes exhibited improved photocatalytic activity. This work demonstrates the importance of versatile functionalization of MOF structures for interface charge transfer on plasmonic photocatalysts.

CHEMISTRY-A EUROPEAN JOURNAL (2022)

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Article Nanoscience & Nanotechnology

Two-Dimensional Porphyrin-Based Covalent Organic Framework with Enlarged Inter-layer Spacing for Tunable Photocatalytic CO2 Reduction

Xinxin Wang et al.

Summary: This study discovers that by introducing bulky phenyl substituents into two-dimensional porphyrin-based covalent organic frameworks (COFs), the axial pi-pi stacking can be reduced, resulting in an enlarged inter-layer spacing. This change improves the surface area and photocatalytic performance of the COFs, further advancing the research on carbon dioxide reduction reaction.

ACS APPLIED MATERIALS & INTERFACES (2022)

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Article Chemistry, Multidisciplinary

Switchable Metal Sites in Metal-Organic Framework MFM-300(Sc): Lewis Acid Catalysis Driven by Metal-Hemilabile Linker Bond Dynamics

Ricardo A. Peralta et al.

Summary: This study unraveled the uncommon reversible and guest-induced metal-hemilabile linker bond dynamics in MOF MFM-300(Sc), which can switch on/off the catalytic open metal sites. The catalytic activity of this MOF was demonstrated and found to be fully reversible, preserving the structure integrity and conversion performance over multiple cycles. Quantum calculations further supported a reaction mechanism driven by Sc-open metal sites.

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION (2022)

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Article Chemistry, Physical

Dynamic weak coordination bonding of chlorocarbons enhances the catalytic performance of a metal-organic framework material

Sun Ho Park et al.

Summary: Chlorocarbons, specifically trichloromethane and dichloromethane, possess lone-pair electrons and the ability to form dynamic weak coordination bonding. Trichloromethane can form coordinative equilibrium with stronger Lewis basic solvents, while dichloromethane differs in coordination strength. Solvents with dynamic weak coordination bonding exhibit higher efficiencies in catalytic reactions.

JOURNAL OF MATERIALS CHEMISTRY A (2022)

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Article Nanoscience & Nanotechnology

Hydrogen Production at a NiO Photocathode Based on a Ruthenium Dye-Cobalt Diimine Dioxime Catalyst Assembly: Insights from Advanced Spectroscopy and Post-operando Characterization

Emmanouil Giannoudis et al.

Summary: This study presents a novel NiO photocathode for photoelectrochemical water splitting for hydrogen production using a new dye sensitization approach. The fast desorption of dyad and low electron transfer efficiency leading to catalyst demetallation were identified as the main barriers limiting system performance and stability.

ACS APPLIED MATERIALS & INTERFACES (2021)

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Article Nanoscience & Nanotechnology

Synthesis of Atomically Thin g-C3N4 Nanosheets via Supercritical CO2 Doping with Single-Atom Cobalt for Photocatalytic Hydrogen Evolution

Wenxiu Li et al.

Summary: Graphitic carbon nitride nanosheets with mesopores were successfully exfoliated using supercritical CO2, with thickness tailored by regulating pressure. Bilayer mesoporous g-C3N4 nanosheets doped with monatomic Co showed enhanced photocatalytic hydrogen evolution performance, suggesting a new perspective for designing inexpensive photocatalysts with unique structures.

ACS APPLIED MATERIALS & INTERFACES (2021)

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Article Nanoscience & Nanotechnology

Rapid Exciton Migration and Amplified Funneling Effects of Multi-Porphyrin Arrays in a Re(I)/Porphyrinic MOF Hybrid for Photocatalytic CO2 Reduction

Sunghan Choi et al.

Summary: This study presents a novel porphyrinic metal-organic framework-Re(I) hybrid photocatalyst with high catalytic activity achieved through efficient exciton migration and funneling, as supported by serial photophysical measurements including decisive Stern-Volmer interpretation.

ACS APPLIED MATERIALS & INTERFACES (2021)

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Article Chemistry, Multidisciplinary

Biocatalytic Cross-Coupling of Aryl Halides with a Genetically Engineered Photosensitizer Artificial Dehalogenase

Yu Fu et al.

Summary: This study successfully achieved the photobiocatalytic cross-coupling of aryl halides using a designer artificial dehalogenase, demonstrating high synthetic value. The research results suggest the optimization of dual catalysis through a genetically encoded chromophore and site-specific modified cofactor, potentially expanding the catalytic repertoire of artificial photoenzymes for various organic transformations.

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2021)

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Article Chemistry, Multidisciplinary

A Visible-Light-Harvesting Covalent Organic Framework Bearing Single Nickel Sites as a Highly Efficient Sulfur-Carbon Cross-Coupling Dual Catalyst

Hui Chen et al.

Summary: This study explores a new COF material that combines photosensitivity and nickel catalytic activity to form a dual-functional catalyst. The catalyst shows excellent catalytic performance in the visible-light-driven catalytic sulfur-carbon cross-coupling reaction. This research demonstrates for the first time the use of a photosensitive COF scaffold and single transition metal sites as a two-component synergistic catalyst in organic transformation.

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION (2021)

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Article Chemistry, Multidisciplinary

Visible-Light Promoted C-O Bond Formation with an Integrated Carbon Nitride-Nickel Heterogeneous Photocatalyst

Arjun Vijeta et al.

Summary: Ni-deposited mesoporous graphitic carbon nitride (Ni-mpg-CNx) is introduced as an inexpensive, robust, easily synthesizable and recyclable material that functions as an integrated dual photocatalytic system. It overcomes the limitations of traditional reactions by providing new opportunities for dual catalysis.

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION (2021)

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Article Chemistry, Multidisciplinary

Site Densities, Rates, and Mechanism of Stable Ni/UiO-66 Ethylene Oligomerization Catalysts

Benjamin Yeh et al.

Summary: Nickel-functionalized UiO-66 metal organic frameworks can oligomerize ethylene without the need for cocatalysts or initiators, maintaining stable rates for over 15 days. Higher ethylene pressures lead to shorter induction periods and more active sites, but only one type of catalytic center is relevant for oligomerization, with the process being sensitive to ethylene pressure. Oligomerization on Ni/UiO-66 follows a first-order reaction with a defined activation energy and is influenced by the number of active sites.

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2021)

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Article Chemistry, Physical

Investigation of the Deactivation and Reactivation Mechanism of a Heterogeneous Palladium(II) Catalyst in the Cycloisomerization of Acetylenic Acids by In Situ XAS

Ning Yuan et al.

Summary: By utilizing in situ X-ray absorption spectroscopy (XAS), researchers uncovered the deactivation mechanism of palladium catalyst in the cycloisomerization of acetylenic acids and developed an improved catalytic protocol that is less prone to deactivation.

ACS CATALYSIS (2021)

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Article Chemistry, Multidisciplinary

Highly Active Heterogeneous Catalyst for Ethylene Dimerization Prepared by Selectively Doping Ni on the Surface of a Zeolitic Imidazolate Framework

Cailing Chen et al.

Summary: This study presents a novel, highly active heterogeneous catalyst Ni-ZIF-8 for the production of 1-butene by ethylene dimerization, exhibiting high catalytic activity and stability surpassing previously reported catalysts. The catalyst's square-planar coordination and site-specific anchoring of Ni contribute to its remarkable performance, following the Cossee-Arlman mechanism as revealed by isotopic labeling experiments.

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2021)

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Article Chemistry, Physical

Ferrocene-Functionalized Polyoxo-Titanium Cluster for CO2 Photoreduction

Jing-Jing Liu et al.

Summary: This study introduced three functionalized polyoxo-titanium clusters (PTCs)-based photocatalysts for CO2 reduction reaction, among which Fcdc-functionalized Ti-8-Fcdc and Ti-6-Fcdc showed efficient CO2-to-HCOO- photoreduction in water with high selectivity and activity. The introduction of Fc-derived ligands was proven to enhance the charge transfer efficiency, significantly impacting the photocatalytic performance of CO2RR.

ACS CATALYSIS (2021)

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Article Chemistry, Multidisciplinary

Weak Coordination Bond of Chloromethane: A Unique Way to Activate Metal Node Within an Unstable Metal-Organic Framework DUT-34

Jinhee Bae et al.

Summary: Activation of metal nodes in MOFs using thermal methods can negatively affect their structural integrity. Instead, this study demonstrates a chemical route activation using chloromethanes to weakly coordinate at the open-metal sites of DUT-34, allowing for safe activation of the framework structure.

BULLETIN OF THE KOREAN CHEMICAL SOCIETY (2021)

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Article Chemistry, Multidisciplinary

Modulating Coordination Environment of Single-Atom Catalysts and Their Proximity to Photosensitive Units for Boosting MOF Photocatalysis

Xing Ma et al.

Summary: A general and facile strategy for the construction of high-loading single-atom catalysts with a tunable coordination microenvironment has been developed based on metal-organic frameworks. The well-accessible and atomically dispersed metal sites possess close proximity to photosensitive units, greatly accelerating charge transfer and promoting photocatalysis. The optimized Ni-1-S/MOF with a unique Ni(I) microenvironment presents excellent photocatalytic H-2 production activity, surpassing other counterparts.

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2021)

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Article Chemistry, Multidisciplinary

Atomically Dispersed Copper Sites in a Metal-Organic Framework for Reduction of Nitrogen Dioxide

Yujie Ma et al.

Summary: Metal-organic framework materials provide an excellent platform for fabricating single-atom catalysts, and this study focuses on atomically dispersed copper sites in UiO-66 for catalytic reduction of NO2. Various characterization techniques confirm the atomic dispersion of copper sites and their significant role in the catalytic process, leading to superior catalytic performance without the need for reductants.

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2021)

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Article Chemistry, Physical

Single Metal-Organic Cage Decorated with an Ir(III) Complex for CO2 Photoreduction

Xiangjuan Qi et al.

Summary: A novel single molecular cage of Ir(III) complex-decorated Zr-MOC has been proposed for CO2 photoreduction, showing high reactivity, selectivity, and apparent quantum yield. The catalytic center is the Ir(III) complex, while the -NH2 in the framework plays a synergetic role in stabilizing the transition state and CO2 adducts, leading to superior performance compared to classical metal-organic framework counterparts.

ACS CATALYSIS (2021)

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Article Chemistry, Physical

Photoredox Heterobimetallic Dual Catalysis Using Engineered Covalent Organic Frameworks

Alberto Lopez-Magano et al.

Summary: The functionalization of an imine-based layered covalent organic framework has allowed the obtention of a heterobimetallated material with photoactive Ir and Ni fragments immobilized within the porous structure. These heterogeneous light-mediated reactions showed enhanced activity and stability compared to analogous homogeneous systems.

ACS CATALYSIS (2021)

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Article Chemistry, Multidisciplinary

Carbon dot/TiO2 nanocomposites as photocatalysts for metallaphotocatalytic carbon-heteroatom cross-couplings

Zhouxiang Zhao et al.

Summary: The study demonstrates that carbon dots immobilized on titanium dioxide are valuable photocatalysts for metallaphotocatalytic carbon-heteroatom cross-couplings, showing wide applicability, high photostability, excellent reusability, and broad absorption across the visible-light spectrum.

GREEN CHEMISTRY (2021)

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Article Chemistry, Applied