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 Fe3+ 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. In addition, the interaction between Ni2+ and Fe3+ allows the electron flow from Ni2+ to Fe3+, further enhancing the NiOOH generation. As a result, the optimized sample exhibits excellent OER activity with a small overpotential of 251 mV at 10 mA cm-2, which is superior to most of the MOF-based OER catalysts reported previously. This work provides a controllable strategy to regulate the structural reconstruction for promoting the OER, which could provide important guidance for the development of more efficient OER electrocatalysts.

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. The challenges and perspectives in the field of MOF/COF hybrids are also provided to inspire more efforts in diversifying this hybrid family and their cross-disciplinary applications.

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 (TAPFy-PhI and TAPB-PhI) have been successfully synthesized via a Schiff base reaction using phthalimide as the acceptor and 1,3,6,8-tetrakis(4-aminophenyl)pyrene (TAPFy) and 1,3,5-tris(4-aminophenyl)benzene (TAPB) as donors. The synthesized COFs exhibited high crystallinity, permanent porosity, excellent chemical stability, suitable band gaps, and broad visible-light absorption. In the presence of ascorbic acid (sacrificial reagent), the TAPFy-PhI COF exhibited an efficient photocatalytic performance with a hydrogen evolution rate of 1763 µmol g-1 h-1. Moreover, the photocatalytic performance was further improved by the addition of Pt (1 wt %) as a cocatalyst, and the hydrogen evolution rate reached 2718 µmol g-1 h-1.

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 Fe3+ 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. Thus, excellent OER activity with current densities of 10 and 100 mA cm-2 are achieved over the defective MOFs at small overpotentials of 286 mV and 365 mV, respectively, which is superior to the commercial RuO2 catalyst and most of the bulk MOFs.

Ultrafine Mo2C 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 Mo2C nanoparticles assembled in N and P-co-doped carbon (Mo2C@NPC) was developed from ZIF-8 encapsulated molybdenum-based polyoxometalates (PMo12) as a highly efficient ORR electrocatalyst and shows excellent performance for zinc-air batteries. The well distribution of the PMo12 in ZIF-8 results in the formation of ultrafine Mo2C nanocrystallites encapsulated in a porous carbon matrix after pyrolysis. Significantly, from experimental and theoretical investigations, the highly porous structure, highly dispersed ultrafine Mo2C and the N and P co-doping in the Mo2C@NPC lead to the remarkable ORR activity with an onset potential of ∼1.01 V, a half-wave potential of ∼0.90 V and a Tafel slope of 51.7 mV dec-1 at 1600 rpm in 0.1 M KOH. In addition, the Mo2C@NPC as an ORR catalyst in zinc-air batteries achieved a high power density of 266 mW cm-2 and a high specific capacity of 780.9 mA h g-1, exceeding that driven by commercial Pt/C. Our results revealed that the porous architecture and ultrafine Mo2C nanocrystallites of the electrocatalysts could facilitate mass transport and increase the accessibility of active sites, thus optimizing their performances in an ORR. The present study provides some guidelines for the design and synthesis of efficient nanostructured electrocatalysts.

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. The MOF exoskeleton coating on the mammalian cells was developed via a one-pot biomimetic mineralization process. With the exoskeleton on, the individual cells were successfully protected against cell protease (i.e., Proteinase K), whereas smaller-sized nutrient transport across the exoskeleton was maintained. Moreover, vital cellular activities mediated by transmembrane GLUT transporter proteins were also unaffected by the MOF exoskeleton formation on the cell surfaces. Altogether, this ability to control the access of specific molecules to a single cell through the porous exoskeleton, along with the cytoprotection provided, should be valuable for biomedical applications of mammalian cells.

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. In the sandwich Ti-MOFs@Pt@DM-LZU1, interfacial pores formed between Ti-MOF@Pt and DM-LZU1, in which Pt nanoparticles (NPs) were encapsulated. The presence of Pt facilitates the charge separation on the photoactive Ti-MOF, while the hydrophobic porous DM-LZU1 shell promotes reactant enrichment. Interfacial pores acting as nanoreactors ensure fast electron and mass transport between the active Pt NPs and the concentrated reactants, leading to high photocatalytic activity. This work presents a new concept for the design of various photocatalysts with considerable activity.

Highly Efficient Porous Carbon Electrocatalyst with Controllable N-Species Content for Selective CO2 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 CO2 reduction reaction (CO2 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. Owing to the large pore sizes, the active sites are well exposed to electrolyte for CO2 RR. The NPC exhibits superior CO2 RR activity with a small onset potential of -0.35 V and a high faradaic efficiency (FE) of 98.4 % towards CO at -0.55 V vs. RHE, one of the highest values among NPC-based CO2 RR electrocatalysts. This work advances an effective and facile way towards highly active and cost-effective alternatives to noble-metal CO2 RR electrocatalysts for practical applications.

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 NH2 -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. Then, the in situ generated hydrogen peroxide serves for the subsequent peroxidase-mimicking reaction that oxidises a chromogenic substrate on the same catalysts in dark to complete the bifunctional oxidase-peroxidase for biomimetic detection of glucose. The bifunctional cascade catalysis is successfully demonstrated in microfluidics for the real-time colorimetric detection of glucose with a low detection limit of 0.8 µM within 30 s. The artificial nanozymes with physiological functions provide the feasible strategies for mimicking the natural enzymes and realizing the biomedical diagnostics with a smart and miniature device.

From Mixed-Metal MOFs to Carbon-Coated Core-Shell Metal Alloy@Metal Oxide Solid Solutions: Transformation of Co/Ni-MOF-74 to CoxNi1-x@CoyNi1-yO@C for the Oxygen Evolution Reaction.

Calcination of the mixed-metal species Co/Ni-MOF-74 leads to the formation of carbon-coated CoxNi1-x@CoyNi1-yO 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. The close proximity of Co and Ni in the mixed-metal Co/Ni-MOF-74 promotes the metal alloying and the formation of a solid solution of metal oxide during the calcination process. The presence of the tightly coated carbon shell prohibits particle agglomeration and stabilizes the CoxNi1-x@CoyNi1-yO nanoparticles in small size. The CoxNi1-x@CoyNi1-yO@C derived from Co/Ni-MOF-74 nanocomposites show superior performance for the oxygen evolution reaction (OER). The use of mixed-metal MOFs as precursors represents a powerful strategy for the fabrication of metal alloy@metal oxide solid solution nanoparticles in small size. This method also holds great promise in the development of multifunctional carbon-coated complex core-shell metal/metal oxides owing to the diversified MOF structures and their flexible chemistry.

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. Since Co was favorably substituted at positions more accessible to the substrate, the mixed-metal Co/Ni-MOF-74 showed superior catalytic performance, compared with pure Co-MOF-74 containing a similar amount of Co. This study provides a facile method to develop solid-solution-like MOFs for heterogeneous catalysis and highlights the great potential of this mixed-metal strategy in the development of MOFs with specific endowed functionalities.

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., 2015, 51, 2056-2059.

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. Unlike that over pure NH2-MIL-125(Ti), in which only formate was produced, both hydrogen and formate were formed over Pt- and Au-loaded NH2-MIL-125(Ti). However, Pt and Au have different effects on the photocatalytic performance for formate production. Compared with pure NH2-MIL-125(Ti), Pt/NH2-MIL-125(Ti) showed an enhanced activity for photocatalytic formate formation, whereas Au has a negative effect on this reaction. To elucidate the origin of the different photocatalytic performance, electron spin resonance (ESR) analyses and density functional theory (DFT) calculations were carried out over M/NH2-MIL-125(Ti).The photocatalytic mechanisms over M/NH2-MIL-125(Ti) (M=Pt and Au) were proposed. For the first time, the hydrogen spillover from the noble metal Pt to the framework of NH2-MIL-125(Ti) and its promoting effect on the photocatalytic CO2 reduction is revealed. The elucidation of the mechanism on the photocatalysis over M/NH2-MIL-125(Ti) can provide some guidance in the development of new photocatalysts based on MOF materials. This study also demonstrates the potential of using noble metal-doped MOFs in photocatalytic reactions involving hydrogen as a reactant, like hydrogenation reactions.

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. Moreover, NH2 -Uio-66(Zr) with mixed ATA and 2,5-diaminoterephthalate (DTA) ligands was prepared and shown to exhibit higher performance for photocatalytic CO2 reduction due to its enhanced light adsorption and increased adsorption of CO2 . This study provides a better understanding of photocatalytic CO2 reduction over MOF-based photocatalysts and also demonstrates the great potential of using MOFs as highly stable, molecularly tunable, and recyclable photocatalysts in CO2 reduction.

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.