Highly effective electrocatalysts promoting CO 2 reduction reaction (CO 2 RR) is extremely desirable to produce value-added chemicals/fuels while addressing current environmental challenges. Herein, we develop a layer-stacked, bimetallic two-dimensional conjugated metalorganic framework (2D c-MOF) with copper-phthalocyanine as ligand (CuN 4) and zinc-bis (dihydroxy) complex (ZnO 4) as linkage (PcCu-O 8-Zn). The PcCu-O 8-Zn exhibits high CO selectivity of 88%, turnover frequency of 0.39 s −1 and long-term durability (>10 h), surpassing thus by far reported MOF-based electrocatalysts. The molar H 2 /CO ratio (1:7 to 4:1) can be tuned by varying metal centers and applied potential, making 2D c-MOFs highly relevant for syngas industry applications. The contrast experiments combined with operando spectroelectrochemistry and theoretical calculation unveil a synergistic catalytic mechanism; ZnO 4 complexes act as CO 2 RR catalytic sites while CuN 4 centers promote the protonation of adsorbed CO 2 during CO 2 RR. This work offers a strategy on developing bimetallic MOF electrocatalysts for synergistically catalyzing CO 2 RR toward syngas synthesis.

Layered two-dimensional (2D) conjugated metalorganic frameworks (MOFs) represent af amily of rising electrocatalysts for the oxygen reduction reaction (ORR), due to the controllable architectures,excellent electrical conductivity,a nd highly exposed well-defined molecular active sites. Herein, we report ac opper phthalocyanine based 2D conjugated MOF with square-planar cobalt bis(dihydroxy) complexes (Co-O 4 )a sl inkages (PcCu-O 8 -Co) and layer-stacked structures prepared via solvothermal synthesis.P cCu-O 8 -Co 2D MOF mixed with carbon nanotubes exhibits excellent electrocatalytic ORR activity (E 1/2 = 0.83 Vv s. RHE, n = 3.93, and j L = 5.3 mA cm À2 )i na lkaline media, which is the record value among the reported intrinsic MOF electrocatalysts. Supported by in situ Raman spectro-electrochemistry and theoretical modeling as well as contrast catalytic tests,w e identified the cobalt nodes as ORR active sites.F urthermore, when employed as ac athode electrocatalyst for zinc-air batteries,P cCu-O 8 -Co delivers am aximum power density of 94 mW cm À2 ,o utperforming the state-of-the-art Pt/C electrocatalysts (78.3 mW cm À2 ).Supportinginformation and the ORCID identification number(s) for the author(s) of this article can be found under: https://doi.

Propane dehydrogenation (PDH) has great potential to meet the increasing global demand for propylene, but the widely used Pt‐based catalysts usually suffer from short‐term stability and unsatisfactory propylene selectivity. Herein, we develop a ligand‐protected direct hydrogen reduction method for encapsulating subnanometer bimetallic Pt–Zn clusters inside silicalite‐1 (S‐1) zeolite. The introduction of Zn species significantly improved the stability of the Pt clusters and gave a superhigh propylene selectivity of 99.3 % with a weight hourly space velocity (WHSV) of 3.6–54 h−1 and specific activity of propylene formation of 65.5 molnormalC3normalH6  gPt−1 h−1 (WHSV=108 h−1) at 550 °C. Moreover, no obvious deactivation was observed over PtZn4@S‐1‐H catalyst even after 13000 min on stream (WHSV=3.6 h−1), affording an extremely low deactivation constant of 0.001 h−1, which is 200 times lower than that of the PtZn4/Al2O3 counterpart under the same conditions. We also show that the introduction of Cs+ ions into the zeolite can improve the regeneration stability of catalysts, and the catalytic activity kept unchanged after four continuous cycles.

The realization of ferromagnetism in semiconductors is an attractive avenue for the development of spintronic applications. Here, we report a semiconducting layered metal-organic framework (MOF), namely K 3 Fe 2 [( 2,3,9,10,16,17,23,24 -octahydroxy phthalocyaninato)Fe] (K 3 Fe 2 [PcFe-O 8 ]) with spontaneous magnetization. This layered MOF features in-plane full π-d conjugation and exhibits semiconducting behavior with a room temperature carrier mobility of 15 ± 2 cm 2 V −1 s −1 as determined by time-resolved Terahertz spectroscopy. Magnetization experiments and 57 Fe Mössbauer spectroscopy demonstrate the presence of long-range magnetic correlations in K 3 Fe 2 [PcFe-O 8 ] arising from the magnetic coupling between iron centers via delocalized π electrons. The sample exhibits superparamagnetic features due to a distribution of crystal size and possesses magnetic hysteresis up to 350 K. Our work sets the stage for the development of spintronic materials exploiting magnetic MOF semiconductors.

Near-infrared (NIR)-II fluorescence agents hold great promise for deep-tissue photothermal therapy (PTT) of cancers, which nevertheless remains restricted by the inherent nonspecificity and toxicity of PTT. In response to this challenge, we herein develop a hydrogen sulfide (H2S)-activatable nanostructured photothermal agent (Nano-PT) for site-specific NIR-II fluorescence-guided PTT of colorectal cancer (CRC). Our in vivo studies reveal that this theranostic Nano-PT probe is specifically activated in H2S-rich CRC tissues, whereas it is nonfunctional in normal tissues. Activation of Nano-PT not only emits NIR-II fluorescence with deeper tissue penetration ability than conventional fluorescent probes but also generates high NIR absorption resulting in efficient photothermal conversion under NIR laser irradiation. Importantly, we establish NIR-II imaging-guided PTT of CRC by applying the Nano-PT agent in tumor-bearing mice, which results in complete tumor regression with minimal nonspecific damages. Our studies thus shed light on the development of cancer biomarker-activated PTT for precision medicine.

The conversion of crystalline metal–organic frameworks (MOFs) into metal compounds/carbon hybrid nanocomposites via pyrolysis provides a promising solution to design electrocatalysts for electrochemical water splitting. However, pyrolyzing MOFs generally involves a complex high‐temperature treatment, which can destroy the coordinated surroundings within MOFs, and as a result not taking their full advantage of their electrolysis properties. Herein, a simple and room‐temperature boronization strategy is developed to convert nickel zeolite imidazolate framework (Ni‐ZIF) nanorods into ultrathin Ni‐ZIF/NiB nanosheets with abundant crystalline–amorphous phase boundaries. The combined experiment, and theoretical calculation results disclose that the ultrathin thickness allows fast electron transfer and ensures increased exposure of surface coordinatively unsaturated active sites while the crystalline–amorphous interface elaborately changes the potential‐determining step to energetically favorable intermediates. As a result, Ni‐ZIF/NiB nanosheets supported on nickel foam (NF) require overpotentials of 67 mV for the hydrogen evolution reaction and 234 mV for the oxygen evolution reaction to achieve a current density of 10 mA cm−2. Remarkably, Ni‐ZIF/NiB@NF as a bifunctional electrocatalyst for overall water splitting enables an alkaline electrolyzer with 10 mA cm−2 at an ultralow cell voltage of 1.54 V. The present work may open a new avenue to the design of MOF‐derived composites for electrocatalysis.

A superwettable nanofibrous membrane with hierarchical structured skin for effective oil/water emulsion separation was fabricated via a combination of electrospinning and electrospraying.

This review focuses on electrospun flexible nanofibrous membranes with tunable wettability for oil/water separation, and future perspectives are discussed.