Synergistic Cooperation of Active Sites in Cu-Incorporated Nitrogen-Doped Porous Carbon for CO Electroreduction to Ethanol.

Selective electroreduction of CO to ethanol has attracted increasing interest. Herein, we report an effective strategy to boost ethanol selectivity from electrocatalytic CO reduction by constructing Cu-incorporated nitrogen-doped porous carbon (Cu-NPC) via pyrolysis of bimetallic CuZn-MOF-74, followed by an etching treatment. Etching processes not only remove large-sized metal particles and create lots of pores in the catalyst but also leave Cu existing mainly as Cu that shows strong electronic interaction with the pyridinic N in NPC.

Steering electron flow by constructing an integrated structure in a metal-organic framework (MOF) iminopyridine units for efficient CO photoreduction to CH and CH.

Selective photoreduction of CO to C products has attracted increasing interest, but it remains challenging. Herein, we reported a novel strategy to steer electron flow by constructing integrated photocatalysts to achieve selective photoreduction of CO to CH and CH. Using iminopyridine units in NH-MIL-125(Ti) (Ti-MOF) as a tag, both the Ru photosensitizer and CuCo active sites were assembled within the Ti-MOF to form the integrated structure.

Electrocatalytic biomass upgrading coupled with hydrogen evolution and CO reduction.

Clean energy production and CO utilization have attracted increasing interest. Electrocatalysis represents an effective way to produce green hydrogen from water and reduce CO to valuable compounds. However, for either the hydrogen evolution reaction (HER) or the CO reduction reaction (CORR), the reaction efficiency is significantly limited by the slow kinetics of the oxygen evolution reaction (OER) at the anode, which consumes most of the input energy.

Accelerating structure reconstruction to form NiOOH in metal-organic frameworks (MOFs) for boosting the oxygen evolution reaction.

Structural reconstruction of electrocatalysts to generate metal hydroxide/oxyhydroxide species is critical for an efficient oxygen evolution reaction (OER), but the controllable regulation of the reconstruction process still remains a challenge. Given the designable nature of metal-organic frameworks (MOFs), herein, we have reported a localized structure disordering strategy to accelerate the structural reconstruction of Ni-BDC to generate NiOOH for boosting the OER. The Ni-BDC nanosheets were modified by Fe and urea to form cracks, which could promote the accessibility of the Ni sites by the electrolyte and thus promote the reconstruction to form NiOOH.

Interfacial chemistries in metal-organic framework (MOF)/covalent-organic framework (COF) hybrids.

Metal-organic frameworks (MOFs) and covalent organic frameworks (COFs) have been attracting tremendous attention in various applications due to their unique structural properties. Recent interest has been focused on their combination as hybrids to enable the engineering of new classes of frameworks with complementary properties. This review gives a comprehensive summary on the interfacial chemistries in MOF/COF hybrids, which play critical roles in their hybridization.

Donor-Acceptor Covalent-Organic Frameworks Based on Phthalimide as an Electron-Deficient Unit for Efficient Visible-Light Catalytic Hydrogen Evolution.

Donor-acceptor two-dimensional covalent-organic frameworks (COFs) have great potential as photocatalysts for hydrogen evolution because of their tunable structures, ordered and strong stacking, high crystallinity, and porosity. Herein, an acceptor unit, namely phthalimide, has been employed for the first time to construct COFs. Two donor-acceptor COFs ( and ) have been successfully synthesized via a Schiff base reaction using phthalimide as the acceptor and 1,3,6,8-tetrakis(4-aminophenyl)pyrene () and 1,3,5-tris(4-aminophenyl)benzene () as donors.

Direct Visualization of Atomic Structure in Multivariate Metal-Organic Frameworks (MOFs) for Guiding Electrocatalysts Design.

The direct utilization of metal-organic frameworks (MOFs) for electrocatalytic oxygen evolution reaction (OER) has attracted increasing interests. Herein, we employ the low-dose integrated differential phase contrast-scanning transmission electron microscopy (iDPC-STEM) technique to visualize the atomic structure of multivariate MOFs (MTV-MOFs) for guiding the structural design of bulk MOFs for efficient OER. The iDPC-STEM images revealed that incorporating Fe or 2-aminoterephthalate (ATA) into Ni-BDC (BDC: benzenedicarboxylate) can introduce inhomogeneous lattice strain that weaken the coordination bonds, which can be selectively cleaved via a mild heat treatment to simultaneously generate coordinatively unsaturated metal sites, conductive Ni@C and hierarchical porous structure.

Ultrafine MoC nanoparticles embedded in an MOF derived N and P co-doped carbon matrix for an efficient electrocatalytic oxygen reduction reaction in zinc-air batteries.

Exploring high-activity electrocatalysts for an oxygen reduction reaction (ORR) is of great significance for a variety of renewable energy conversion and storage technologies. Here, ultrafine MoC nanoparticles assembled in N and P-co-doped carbon (MoC@NPC) was developed from ZIF-8 encapsulated molybdenum-based polyoxometalates (PMo) as a highly efficient ORR electrocatalyst and shows excellent performance for zinc-air batteries. The well distribution of the PMo in ZIF-8 results in the formation of ultrafine MoC nanocrystallites encapsulated in a porous carbon matrix after pyrolysis.

Rapid Single-Step Growth of MOF Exoskeleton on Mammalian Cells for Enhanced Cytoprotection.

Mammalian cells are promising agents for cell therapy, diagnostics, and drug delivery. For full utilization of the cells, development of an exoskeleton may be beneficial to protecting the cells against the environmental stresses and cytotoxins to which they are susceptible. We report here a rapid single-step method for growing metal-organic framework (MOF) exoskeletons on a mammalian cell surface under cytocompatible conditions.

Hydrophobic MOFs@Metal Nanoparticles@COFs for Interfacially Confined Photocatalysis with High Efficiency.

Converting solar energy to chemical energy via photocatalysis has attracted increasing interest. Simultaneously realizing efficient charge separation and fast reactant/product diffusion/transport is highly significant for improving the photocatalytic activity, which however is difficult. Herein, we reported an interfacially confined strategy by constructing interfacial pores as nanoreactors between metal-organic frameworks (MOFs) and covalent organic frameworks (COFs) with controlled surface wettability for efficient photocatalysis.

Highly Efficient Porous Carbon Electrocatalyst with Controllable N-Species Content for Selective CO Reduction.

We report a straightforward strategy to design efficient N doped porous carbon (NPC) electrocatalyst that has a high concentration of easily accessible active sites for the CO reduction reaction (CO RR). The NPC with large amounts of active N (pyridinic and graphitic N) and highly porous structure is prepared by using an oxygen-rich metal-organic framework (Zn-MOF-74) precursor. The amount of active N species can be tuned by optimizing the calcination temperature and time.

Pore-Surface Engineering by Decorating Metal-Oxo Nodes with Phenylsilane to Give Versatile Super-Hydrophobic Metal-Organic Frameworks (MOFs).

Hydrophobization of metal-organic frameworks (MOFs) is important to push forward their practical use and thus has attracted increasing interest. In contrast to the previous reports, which mainly focused on the modification of organic ligands in MOFs, herein, we reported a novel strategy to decorate the metal-oxo nodes of MOFs with phenylsilane to afford super-hydrophobic NH -UiO-66(Zr), which shows highly improved base resistance and holds great promise in versatile applications, such as organic/water separation, self-cleaning, and liquid-marble fabrication. This work demonstrates the first attempt at metal-oxo node modification for super-hydrophobic MOFs, advancing a new concept in the design of MOFs with controlled wettability for practical applications.

Modified carbon nitride nanozyme as bifunctional glucose oxidase-peroxidase for metal-free bioinspired cascade photocatalysis.

Nanomaterials-based biomimetic catalysts with multiple functions are necessary to address challenges in artificial enzymes mimicking physiological processes. Here we report a metal-free nanozyme of modified graphitic carbon nitride and demonstrate its bifunctional enzyme-mimicking roles. With oxidase mimicking, hydrogen peroxide is generated from the coupled photocatalysis of glucose oxidation and dioxygen reduction under visible-light irradiation with a near 100% apparent quantum efficiency.

From Mixed-Metal MOFs to Carbon-Coated Core-Shell Metal Alloy@Metal Oxide Solid Solutions: Transformation of Co/Ni-MOF-74 to CoNi@CoNiO@C for the Oxygen Evolution Reaction.

Calcination of the mixed-metal species Co/Ni-MOF-74 leads to the formation of carbon-coated CoNi@CoNiO with a metal core diameter of ∼3.2 nm and a metal oxide shell thickness of ∼2.4 nm embedded uniformly in the ligand-derived carbon matrix.

Mixed-Metal Strategy on Metal-Organic Frameworks (MOFs) for Functionalities Expansion: Co Substitution Induces Aerobic Oxidation of Cyclohexene over Inactive Ni-MOF-74.

Different amounts of Co-substituted Ni-MOF-74 have been prepared via a post-synthetic metal exchange. Inductively coupled plasma mass spectrometry, powder X-ray diffraction (XRD), N2 adsorption/desorption, and extended X-ray absorption fine structure (EXAFS) analyses indicated the successful metathesis between Co and Ni in Ni-MOF-74 to form the solid-solution-like mixed-metal Co/Ni-MOF-74. It was found that introduction of active Co into the Ni-MOF-74 framework enabled the inert Ni-MOF-74 to show activity for cyclohexene oxidation.

Correction: Introduction of a mediator for enhancing photocatalytic performance via post-synthetic metal exchange in metal-organic frameworks (MOFs).

Correction for 'Introduction of a mediator for enhancing photocatalytic performance via post-synthetic metal exchange in metal-organic frameworks (MOFs)' by Dengrong Sun et al., Chem. Commun.

Construction of a supported Ru complex on bifunctional MOF-253 for photocatalytic CO2 reduction under visible light.

A MOF-253 supported active Ru carbonyl complex (MOF-253-Ru(CO)2Cl2) was constructed for photocatalytic CO2 reduction under visible light irradiation. Its performance can be further improved by immobilization as a photosensitizer. This study highlights the great potential of using MOFs as a solid ligand and platform for the assembly of a complicated catalytic system.

Introduction of a mediator for enhancing photocatalytic performance via post-synthetic metal exchange in metal-organic frameworks (MOFs).

Ti-substituted NH2-Uio-66(Zr/Ti) prepared by using a post-synthetic exchange (PSE) method showed enhanced photocatalytic performance for both CO2 reduction and hydrogen evolution under visible light. Density functional theory (DFT) calculations and electron spin resonance (ESR) results reveal that the introduced Ti substituent acts as a mediator to facilitate electron transfer, which results in enhanced performance.

Noble metals can have different effects on photocatalysis over metal-organic frameworks (MOFs): a case study on M/NH₂-MIL-125(Ti) (M=Pt and Au).

M-doped NH2-MIL-125(Ti) (M=Pt and Au) were prepared by using the wetness impregnation method followed by a treatment with H2 flow. The resultant samples were characterized by powder X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), X-ray absorption fine structure (XAFS) analyses, N2-sorption BET surface area, and UV/Vis diffuse reflectance spectroscopy (DRS). The photocatalytic reaction carried out in saturated CO2 with triethanolamine (TEOA) as sacrificial agent under visible-light irradiations showed that the noble metal-doping on NH2-MIL-125(Ti) promoted the photocatalytic hydrogen evolution.

Studies on photocatalytic CO(2) reduction over NH2 -Uio-66(Zr) and its derivatives: towards a better understanding of photocatalysis on metal-organic frameworks.

Metal-organic framework (MOF) NH2 -Uio-66(Zr) exhibits photocatalytic activity for CO2 reduction in the presence of triethanolamine as sacrificial agent under visible-light irradiation. Photoinduced electron transfer from the excited 2-aminoterephthalate (ATA) to Zr oxo clusters in NH2 -Uio-66(Zr) was for the first time revealed by photoluminescence studies. Generation of Zr(III) and its involvement in photocatalytic CO2 reduction was confirmed by ESR analysis.

An amine-functionalized titanium metal-organic framework photocatalyst with visible-light-induced activity for CO2 reduction.

Let your light shine: the photocatalytic reduction of carbon dioxide to the formate anion under visible light irradiation is for the first time realized over a photoactive Ti-containing metal-organic framework, NH(2)-MIL-125(Ti), which is fabricated by a facile substitution of ligands in the UV-responsive MIL-125(Ti) material.