Highly Efficient Photocatalysts: Polyoxometalate Synthons Enable Tailored CdS-MoS2 Morphologies and Enhanced H2 Evolution.

The development of photocatalysts toward highly efficient H2 evolution reactions is a feasible strategy to achieve the effective conversion of solar energy and meet the increasing demand for new energy. To this end, we prepared two different CdS-MoS2 photocatalysts with unique morphologies ranging from hexagonal prisms to tetragonal nanotubes by carefully tuning polyoxometalate synthons. These two photocatalysts, namely, CdS-MoS2-1 and CdS-MoS2-2, both exhibited remarkable photocatalytic efficiency in H2 generation, among which CdS-MoS2-2 showed superior performance. In fact, the best catalytic hydrogen desorption rate of CdS-MoS2-2 is as high as 1815.5 µmol g-1 h-1. Such performance is superior to twice that of single CdS and almost four times that of pure MoS2. This obvious enhancement can be accredited to the highly open nanotube morphology and highly dispersed heterometallic composition of CdS-MoS2-2, which represents an excellent example of the highest noble-metal-free H2 evolution photocatalysts reported so far. Taken together, these findings suggest that the development of highly dispersed heterometallic catalysts is an auspicious route to realize highly efficient conversion of solar energy and that CdS-MoS2-2 represents a major advance in this field.

Ultrasensitive Electrochemical Detection of Butylated Hydroxy Anisole via Metalloporphyrin Covalent Organic Frameworks Possessing Variable Catalytic Active Sites.

Three novel two-dimensional metalloporphyrin COFs (MPor-COF-366, M = Fe, Mn, Cu) were fabricated by changing the metal atoms in the center of the porphyrin framework. The physicochemical characteristics of MPor-COF-366 (M = Fe, Mn, Cu) composites were fully analyzed by diverse electron microscopy and spectroscopy. Under optimal conditions, experiments on determining butylated hydroxy anisole (BHA) at FePor-COF-366/GCE were conducted using differential pulse voltammetry (DPV). It is noted that the FePor-COF-366/GCE sensor showed excellent electrocatalytic performance in the electrochemical detection of BHA, compared with MnPor-COF-366/GCE and CuPor-COF-366/GCE. A linear relationship was obtained for 0.04-1000 µM concentration of BHA, with a low detection limit of 0.015 µM. Additionally, the designed sensor was successfully employed to detect BHA in practical samples, expanding the development of COF-based composites in electrochemical applications.

Beyond Pristine Metal-Organic Frameworks: Preparation of Hollow MOFs and Their Composites for Catalysis, Sensing, and Adsorption Removal Applications.

Metal-organic frameworks (MOFs) have been broadly applied to numerous domains with a substantial surface area, tunable pore size, and multiple unsaturated metal sites. Recently, hollow MOFs have greatly attracted the scientific community due to their internal cavities and gradient pore structures. Hollow MOFs have a higher tunability, faster mass-transfer rates, and more accessible active sites when compared to traditional, solid MOFs. Hollow MOFs are also considered to be candidates for some functional material carriers. For example, composite materials such as hollow MOFs and metal nanoparticles, metal oxides, and enzymes have been prepared. These composite materials integrate the characteristics of hollow MOFs with functional materials and are broadly used in many aspects. This review describes the preparation strategies of hollow MOFs and their composites as well as their applications in organic catalysis, electrochemical sensing, and adsorption separation. Finally, we hope that this review provides meaningful knowledge about hollow-MOF composites and their derivatives and offers many valuable references to develop hollow-MOF-based applied materials.

Superaerophobic P-doped Ni(OH)2/NiMoO4 hierarchical nanosheet arrays grown on Ni foam for electrocatalytic overall water splitting.

Transition metal (TM) oxides and hydroxides are one of the important candidates for the development of durable and low-cost electrocatalysts towards water splitting. The key issue is exploring effective methods to improve their electrocatalytic activity. Herein, we report a new type of P-doped Ni(OH)2/NiMoO4 hierarchical nanosheet array (abbr. P-Ni(OH)2/NiMoO4) grown on Ni foam (NF), which can act as a highly efficient electrocatalyst towards overall water splitting. Such a composite was obtained by a three-step preparation process. In the first two hydrothermal reactions, the crystalline Ni(OH)2 hierarchical nanosheet arrays were grown on NF and then the low crystallinity NiMoO4 was grafted on the Ni(OH)2 nanosheets. In the third phosphorization step, P element was doped into the composite Ni(OH)2/NiMoO4. Electrocatalytic experiments show that P-Ni(OH)2/NiMoO4 possesses a smaller overpotential (60 mV) and lower Tafel slope (130 mV dec-1) toward HER in 1 M KOH. When it was employed as an integrated water splitting catalyst, only a potential of 1.55 V was required to achieve a current density of 10 mA cm-2. This catalytic activity is even better than those of electrolyzers constructed with noble metals Pt/C∥IrO2. The superior electrocatalytic performance of P-Ni(OH)2/NiMoO4 can be attributed to the high quality of crystalline Ni(OH)2 nanosheet arrays grown on NF, which dramatically improve the conductivity. Furthermore, the hierarchical structure not only increases the surface area and exposes more catalytically active sites, but also provides a superaerophobic surface, which helps to accelerate the release of generated bubbles. Moreover, the synergistic effects between P-Ni(OH)2 and P-NiMoO4 efficiently promote the HER and OER processes also. This work may suggest new a way to explore TM oxide/hydroxide-based durable electrocatalysts with highly efficient electrocatalytic activities towards overall water splitting.

Polyoxometalate-Based Metal-Organic Frameworks for Selective Oxidation of Aryl Alkenes to Aldehydes.

Polyoxometalates (POMs) show considerable catalytic performance toward the selective oxidation of alkenes to aldehydes, which is commercially valuable for the production of pharmaceuticals, dyes, perfumes, and fine chemicals. However, the low specific surface area of POMs as heterogeneous catalysts and poor recyclability as homogeneous catalysts have hindered their wide application. Dispersing POMs into metal-organic frameworks (MOFs) for the construction of POM-based MOFs (POMOFs) suggests a promising strategy to realize the homogeneity of heterogeneous catalysis. Herein, we report two new POMOFs with chemical formulas of [Co(BBTZ)2][H3BW12O40]·10H2O (1) and [Co3(H2O)6(BBTZ)4][BW12O40]·NO3·4H2O (2) (BBTZ = 1,4-bis(1,2,4-triazol-1-ylmethyl)benzene) for the selective oxidation of alkenes to aldehydes. Compound 1 possesses a non-interpenetrated three-dimensional (3D) cds-type open framework with a 3D channel system. Compound 2 displays a 3D polyrotaxane framework with one-dimensional channels along the [100] direction. In the selective oxidation of styrene into benzaldehyde, compound 1 can achieve a 100% conversion in 4 h with 96% selectivity toward benzaldehyde, which is superior to that of compound 2. A series of control experiments reveal that the co-role of [BW12O40]5- and Co2+ active center as well as a more open framework feature co-promote the catalytic property of the POMOFs in this case. This work may suggest a new option for the development of POMOF catalysts in the selective oxidation of alkenes.

Polyoxometalate and Resin-Derived P-Doped Mo2 C@N-Doped Carbon as a Highly Efficient Hydrogen-Evolution Reaction Catalyst at All pH Values.

A new type of P-doped Mo2 C coated by N-doped carbon (P-Mo2 C@NC) has been successfully prepared by calcining a mixture of H3 [PMo12 O40 ] polyoxometalates (POMs) and urea-formaldehyde resin under an N2 atmosphere. Urea-formaldehyde resin not only serves as the carbon source to ensure carbonization but also facilitates the uniform distribution of POM precursors, which efficiently avoid the aggregation of Mo2 C particles at high temperatures. TEM analysis revealed that the average diameter of the Mo2 C particles was about 10 nm, which is coated by a few-layer N-doped carbon sheet. The as-prepared P-Mo2 C@NC displayed excellent hydrogen-evolution reaction (HER) performance and long-term stability in all pH environments. To reach a current density of 10 mA cm-2 , only 109, 159, and 83 mV were needed for P-Mo2 C@NC in 0.5 m H2 SO4 (pH 0), 0.1 m phosphate buffer (pH 7), and 1 m KOH (pH 14), respectively. This could provide a high-yield and low-cost method to prepare uniform nanosized molybdenum carbides with highly efficient and stable HER performance.

A New Polyoxometalate (POM)-Based Composite: Fabrication through POM-Assisted Polymerization of Dopamine and Properties as Anode Materials for High-Performance Lithium-Ion Batteries.

Organic substrates are indispensable in the fabrication of multifunctional polyoxometalate (POM)-based composites for various applications. A new molybdovanadophosphoric heteropolyacid (PMo10 V2 )-based polydopamine (PDA) composite (PMo10 V2 /PDA) is first synthesized through a facile, in situ polymerization method under hydrothermal conditions, without the addition of extra buffer solution. The obtained PMo10 V2 /PDA composite shows homogeneous microsphere morphology. Through utilization of the adhesive ability of PDA, the composite can be used as an anode material without additional binder for rechargeable lithium-ion batteries. Excellent electrochemical performances are obtained, with a high, stable specific capacity of 915.3 mA h g-1 at a current density of 100 mA g-1 , remarkable rate capability, and good cycling stability (≈93 % capacity retention after 300 cycles at a high current density of 1000 mA g-1 ).

MoP/Mo2C@C: A New Combination of Electrocatalysts for Highly Efficient Hydrogen Evolution over the Entire pH Range.

During the exploration of highly efficient noble-metal-free electrocatalysts for the hydrogen evolution reaction (HER), a promising and challenging strategy is to fabricate composite nanocatalysts by finely tuning metal and/or nonmetal element components. Herein, we report a new HER electrocatalyst, which is composed of molybdenum phosphide and molybdenum carbide composite nanoparticles (NPs) coated by few-layer N-doped graphitic carbon shells (denoted as MoP/Mo2C@C). Such a new combination mode of electrocatalysts is realized by a one-step annealing route with the mixture of a Mo/P-based polyoxometalate (POM) and dicyandiamide. On the basis of this method, the simultaneous phosphorization and carbonization in a nanoscale confined space can be easily achieved by the use of POM as the molecular-element-regulating platform. MoP/Mo2C@C exhibits more remarkable HER performance over the whole pH range than those of MoP, Mo2C, and the physical mixture of MoP and Mo2C. The low overpotentials of 89, 136, and 75 mV were obtained at a current density of 10 mA cm-2 in the media of pH = 0, 7, and 14, respectively. Furthermore, MoP/Mo2C@C shows a long-term durability for 14 h over the entire pH range (0-14). Because of the protection of carbon shells, such composite electrocatalyst also possesses better transition-metal tolerance exemplified by Fe2+, Co2+, and Ni2+ than that of 20% commercial Pt/C. This work demonstrates the advantage of POM precursors in adjusting the component and properties of nanoscale composite electrocatalysts for HER, which may suggest new options for the fabrication of highly efficient composite electrocatalysts.

Visible light inactivation of E. coli, Cytotoxicity and ROS determination of biochemically capped gold nanoparticles.

The formation of metal nanoparticles is one of the most vast and intensifying research areas in favor of prospective applications for the advancement of new technologies. It is a well-founded, significant feature of green chemistry that making marvelous interconnection between nano-biotechnology and microbial biotechnology. In the present research, the aqueous extract of medicinally important plant Coptis Chinensis (in Chinese called "gold thread") was applied for the synthesis of gold nanoparticles (Au-NPs). The crystalline structure, size, shape and dispersion of Au-NPs were confirmed by using various characterization techniques i.e. X-ray Diffraction (XRD), High Resolution Transmission Electron Microscope (HRTEM) and Energy Dispersive X-ray (EDX). Well dispersed face centered cubic crystalline structures were obtained in the this contribution. The possible phyto-chemicals involved in the reduction and stabilization of Au-NPs were confirmed by Fourier Transform Infrared Spectroscopy (FT-IR). The prepared NPs were tested against highly drug resistance bacterium Escherichia coli both in light and dark. The results illustrated that the antibacterial efficiency of photo irradiated Au-NPs was several times higher than in dark Au-NPs. The zone of inhibition for irradiated Au-NPs was19 ± 0.5 mm, which was higher than in dark 14 ± 0.4 mm. This high antibacterial activity of photo irradiated Au-NPs are due to the production of reactive oxygen species which is responsible for the inhibition of bacteria.

Antimony-dependent expansion for the Keggin heteropolyniobate family.

Nine new Sb-bicapped α-Keggin-type heteropolyoxoniobates (HPNb) were synthesized under hydrothermal conditions. Among them, the As-centered HPNb was never reported before, and the two dimer compounds are the biggest isolated HPNbs at present.