Heterostructures composed of two-dimensional black phosphorus (2D BP) with unique physical/chemical properties are of great interest. Herein, we report a simple solvothermal method to synthesize in-plane BP/Co P heterostructures for electrocatalysis. By using the reactive edge defects of the BP nanosheets as the initial sites, Co P nanocrystals are selectively grown on the BP edges to form the in-plane BP/Co P heterostructures. Owing to disposition on the original defects of BP, Co P improves the conductivity and offers more active electrocatalytic sites, so that the BP/Co P nanosheets exhibit better and more stable electrocatalytic activities in the hydrogen evolution and oxygen evolution reactions. Our work not only extends the application of BP to electrochemistry, but also provides a new idea to improve the performance of BP by utilization of defects. Furthermore, this strategy can be extended to produce other BP heterostructures to expand the corresponding applications.

Heterostructures composed of two-dimensional black phosphorus (2D BP) with unique physical/chemical properties are of great interest. Herein, we report as imple solvothermal method to synthesize in-plane BP/Co 2 Ph eterostructures for electrocatalysis.B yu sing the reactive edge defects of the BP nanosheets as the initial sites,C o 2 Pn anocrystals are selectively grown on the BP edges to form the inplane BP/Co 2 Ph eterostructures.O wing to disposition on the original defects of BP,C o 2 Pi mproves the conductivity and offers more active electrocatalytic sites,s ot hat the BP/Co 2 P nanosheets exhibit better and more stable electrocatalytic activities in the hydrogen evolution and oxygen evolution reactions.Our work not only extends the application of BP to electrochemistry,b ut also provides an ew idea to improve the performance of BP by utilization of defects.Furthermore,this strategy can be extended to produce other BP heterostructures to expand the corresponding applications.

An efficient metal‐free photocatalyst composed of black phosphorus (BP) and graphitic carbon nitride (CN) is prepared on a large scale by ball milling. Using economical urea and red phosphorus (RP) as the raw materials, the estimated materials cost of BP/CN is 0.235 Euro per gram. The BP/CN heterostructure shows efficient charge separation and possesses abundant active sites, giving rise to excellent photocatalytic H2 evolution and rhodamine B (RhB) degradation efficiency. Without using a co‐catalyst, the metal‐free BP/CN emits H2 consistently at a rate as large as 786 µmol h−1 g−1 and RhB is decomposed in merely 25 min during visible‐light irradiation. The corresponding electron/hole transfer and catalytic mechanisms are analyzed and described. The efficient metal‐free catalyst is promising in visible‐light photocatalysis and the simple ball‐milling synthetic method can be readily scaled up.

Two simple water soluble [FeFe]-H2ase mimic systems (I and II) were designed to understand the basic principles governing photocatalytic H2 evolution.

New coordination polymers of cobalt(II), namely, [Co(μ 4 -cpna)- 4), have been generated under hydrothermal conditions from CoCl 2 •6H 2 O, two different multifunctional pyridine-carboxylic acids {H 2 cpna: 5-(4-carboxyphenoxy)nicotinic acid; H 3 dppa: 5-(3,4-dicarboxylphenyl)picolinic acid}, and optional N,N-supporting ligands {phen: 1,10-phenanthroline; 4,4′-bipy: 4,4′-bipyridine} acting as mediators of crystallization. These Co(II) coordination polymers (CPs) have been obtained as stable crystalline materials and characterized by conventional solid-state techniques, including X-ray crystallography. The obtained products are 3D metal−organic frameworks (MOFs 1 and 4) or 2D coordination polymers (CPs 2 and 3). Analysis of the topologies of simplified nets has revealed the sra (1), fes (2), and 3,4L13 (3) networks, in addition to a very complex topologically unique framework in 4. An observed diversity of structures is driven by types of carboxylate building blocks and crystallization mediators. Thermal stability and magnetic and catalytic properties of 1−4 have also been studied. In fact, the Co(II) compounds act as heterogeneous catalysts for the oxidation of alcohols with tBuOOH (tert-butylhydroperoxide) under mild conditions. Compound 2 features a good catalytic activity (up to 45% yield) in the oxidation of 1-indanol to 1-indanone. Finally, products 1−4 broaden a still very small number of CPs or MOFs driven by the present type of multifunctional pyridine-carboxylic acids (H 2 cpna, H 2 dppa).

Solar H2 evolution of CdSe QDs can be significantly enhanced simply by introducing a suitable hole‐accepting‐ligand for achieving efficient hole extraction and transfer at the nanoscale interfaces, which opens an effective pathway for dissociation of excitons to generate long‐lived charge separation, thus improving the solar‐to‐fuel conversion efficiency.

A three-component aqueous reaction system comprising copper(II) acetate (metal node), poly(carboxylic acid) with a phenylpyridine or biphenyl core (main building block), and 1,10-phenanthroline (crystallization mediator) was investigated under hydrothermal conditions. As a result, four new coordination compounds were self-assembled, namely,where H 2 cpna = 5-(2′-carboxylphenyl)nicotinic acid, H 3 btc = biphenyl-2,4,4′tricarboxylic acid, H 3 cpic = 4-(5-carboxypyridin-2-yl)isophthalic acid, H 3 cptc = 2-(4-carboxypyridin-3-yl)terephthalic acid, and phen = 1,10-phenanthroline. Crystal structures of compounds 1−3 reveal that they are 1D coordination polymers with a ladder, linear, or double-chain structure, while product 4 is a 0D hexanuclear complex. All of the structures are extended further [1D → 2D (1 and 2), 1D → 3D (3), and 0D → 3D (4)] into hydrogen-bonded networks. The type of a multicarboxylate building block has a considerable effect on the final structures of 1−4. The magnetic behavior and thermal stability of 1−4 were also investigated. Besides, these copper(II) derivatives efficiently catalyze the oxidation of cycloalkanes with hydrogen peroxide under mild conditions. The obtained products are the unique examples of copper derivatives that were assembled from H 2 cpna, H 3 btc, H 3 cpic, and H 3 cptc, thus opening up their use as multicarboxylate ligands toward the design of copper−organic architectures.

An amphiphilic polymeric micelle is utilized as a microreactor to load a hydrophobic [FeFe]-hydrogenase mimic in water. The local concentration enhancement and strong interaction between the mimic and the photosensitizer as well as the water-mediated fast proton migration caused by the microreactor improve photocatalytic hydrogen production remarkably in water.