Fullerene on non-iron cluster-matrix co-catalysts promotes collaborative H and N activation for ammonia synthesis.

Developing highly effective catalysts for ammonia (NH) synthesis is a challenging task. Even the current, prevalent iron-derived catalysts used for industrial NH synthesis require harsh reaction conditions and involve massive energy consumption. Here we show that anchoring buckminsterfullerene (C) onto non-iron transition metals yields cluster-matrix co-catalysts that are highly efficient for NH synthesis.

Facile synthesis of defect-rich interfacial Mo/MoO for efficient peroxymonosulfate activation and refractory pollutants degradation.

Peroxymonosulfate-based advanced oxidation process (PMS-AOP) has shown great potential in sewage purification, and catalyst development capable of efficient PMS activation is a key while challenging element. Herein we reported a facile electro-explosive route to synthesize the oxygen vacancy (Vo)-enriched Mo/MoO without using chemical reagents. The detailed studies suggested that the synergy of Mo active site and Vo in the catalyst significantly boosted the activation kinetics of PMS.

Precious-Metal-Free Mo-MXene Catalyst Enabling Facile Ammonia Synthesis Via Dual Sites Bridged by H-Spillover.

To date, NH synthesis under mild conditions is largely confined to precious Ru catalysts, while nonprecious metal (NPM) catalysts are confronted with the challenge of low catalytic activity due to the inverse relationship between the N dissociation barrier and NH ( = 1-3) desorption energy. Herein, we demonstrate NPM (Co, Ni, and Re)-mediated MoCT MXene (where T denotes the OH group) to achieve efficient NH synthesis under mild conditions. In particular, the NH synthesis rate over Re/MoCT and Ni/MoCT can reach 22.

Carbazolic Conjugated Microporous Polymers for Photocatalytic Organic Transformations.

Heterogeneous photocatalysis have been deemed as a versatile and colorful platform for exploring efficient transformation systems. Henceforth, the design of photocatalysts underpins a wide range of research interests. By virtue of synthetic versatility, stability, non-toxicity, purely organic properties, tunable semiconductive structures, and remarkable visible-light absorbance, conjugated microporous polymers (CMPs) have emerged as an attractive new class of semiconductor materials that show great potential for tackling important energy and environmental challenges.

Mixing Characteristic and High-Throughput Synthesis of Cadmium Sulfide Nanoparticles with Cubic Hexagonal Phase Junctions in a Chaotic Millireactor.

A four-stage oscillating feedback millireactor with splitters (S-OFM) was designed to improve the mixing performance based on chaotic advection. Three-dimensional CFD simulations were used to investigate its flow characteristics and mixing performance, and the generation mechanisms of secondary flows were examined. The results show that the mixing index (MI) increased with the increase in the Reynolds number (), and MI could reach 99.

WO Photoanode with Predominant Exposure of {202} Facets for Enhanced Selective Oxidation of Glycerol to Glyceraldehyde.

The photoelectrocatalytic (PEC) oxidation of glycerol into highly value-added products is attractive, but it is extremely challenging to limit the oxidation products to the valuable C3 chemicals. The hole concentration and surface atomic arrangement of a photoanode can be modulated by controlling facet exposure, thus tuning the activity and selectivity. Herein, we report for the first time the formation of a WO photoanode with predominant exposure of {202} facets by a secondary hydrothermal method.

Enhanced photocatalytic activity of the direct Z-scheme black phosphorus/BiOX (X = Cl, Br, I) heterostructures.

Bismuth oxyhalides (BiOX), as a typical photocatalytic material, have attracted much attention due to their unique layered structure, non-toxicity and excellent stability. However, the photocatalytic performance of BiOX is limited by their weak light absorption ability and rapid recombination of photo-generated carriers. In the present work, first-principles calculations have been performed to comprehensively explore the structural, electronic and optical properties of black phosphorus (BP)/BiOX (X = Cl, Br, I) heterostructures, revealing the inherent reasons for their enhanced photocatalytic performance.

Thickness-induced band-gap engineering in lead-free double perovskite CsAgBiBr for highly efficient photocatalysis.

In recent years, two-dimensional (2D) lead-free double perovskites have been attracting much attention because of their unique performance in photovoltaic solar cells and photocatalysis. Nonetheless, how thickness affects the photoelectric properties of lead-free double perovskite remains unclear. In this work, by means of density functional theory (DFT) with a spin orbit coupling (SOC) effect, we have investigated the electronic and optical properties systemically, including band structures, carrier mobility, optical absorption spectra, exciton-binding energies, band edges alignment and molecule adsorption performance of Cs2AgBiBr6 with different thicknesses.

Activity and Stability Boosting of an Oxygen-Vacancy-Rich BiVO Photoanode by NiFe-MOFs Thin Layer for Water Oxidation.

The introduction of oxygen vacancies (Ov) has been regarded as an effective method to enhance the catalytic performance of photoanodes in oxygen evolution reaction (OER). However, their stability under highly oxidizing environment is questionable but was rarely studied. Herein, NiFe-metal-organic framework (NiFe-MOFs) was conformally coated on oxygen-vacancy-rich BiVO (Ov-BiVO ) as the protective layer and cocatalyst, forming a core-shell structure with caffeic acid as bridging agent.

Iodine-Catalyzed Synthesis of '-Chelate Organoboron Aminoquinolate.

We disclose a novel method for the synthesis of fluorescent ,'-chelate organoboron compounds in high efficiency by treatment of aminoquinolates with NaBAr/R'COOH in the presence of an iodine catalyst. These compounds display high air and thermal stability. A possible catalytic mechanism based on the results of control experiments has been proposed.

Zeolite-seed-directed Ru nanoparticles highly resistant against sintering for efficient nitrogen activation to ammonia.

To stabilize Ru nanoparticles against sintering is an urgent problem in the utilization of Ru-based catalysts for NH synthesis. In the present study, we used Ru-containing ZSM-5 as seeds to crystallize ZSM-5, and the resulted Ru@ZSM-5 catalyst is highly resistant against Ru sintering. According to the results of diffuse reflectance infrared fourier transform spectroscopy (DRIFTS) and transmission electron microscopy (TEM) analyses, the average size of Ru nanoparticles is around 3.

Nickel-Catalyzed Decarbonyloxidation of 3-Aryl Benzofuran-2()-ones to 2-Hydroxybenzophenones.

We have developed a protocol to facilitate the nickel-catalyzed decarbonyloxidation of 3-aryl benzofuran-2()-ones to 2-hydroxybenzophenones under mild conditions, which is an efficient approach for the decarbonyloxidation of lactones in organic synthesis. A diverse range of substrates can undergo C(O)-O/C(O)-C bond cleavage to generate the target products in good yields. These 2-hydroxybenzophenones can be converted into a variety of compounds via reactions such as esterification, cyclization, and reduction.

Iron-Based Metal-Organic Frameworks as Platform for HS Selective Conversion: Structure-Dependent Desulfurization Activity.

Three classical Fe-MOFs, viz., MIL-100(Fe), MIL-101(Fe), and MIL-53(Fe), were synthesized to serve as platforms for the investigation of structure-activity relationship and catalytic mechanism in the selective conversion of HS to sulfur. The physicochemical properties of the Fe-MOFs were characterized by various techniques.

Insight into dynamic and steady-state active sites for nitrogen activation to ammonia by cobalt-based catalyst.

The industrial synthesis of ammonia (NH) using iron-based Haber-Bosch catalyst requires harsh reaction conditions. Developing advanced catalysts that perform well at mild conditions (<400 °C, <2 MPa) for industrial application is a long-term goal. Here we report a Co-N-C catalyst with high NH synthesis rate that simultaneously exhibits dynamic and steady-state active sites.

CFSONa-Mediated, UV-Light-Induced Friedel-Crafts Alkylation of Indoles with Ketones/Aldehydes and Bioactivities of Products.

A concise, one-step route to produce 3,3'-diindolylmethanes (DIMs) from simple indoles and ketones or aldehydes is reported. The key step is the ready formation of indole derivatives that involves the in situ conversion of CFSONa reagent to ·CF under oxygen or air (1.0 atm) and UV irradiation.

How to achieve a highly selective yet simply available vanadium phosphorus oxide-based catalyst for sustainable acrylic acid production via acetic acid-formaldehyde condensation.

A series of unsupported and supported vanadium phosphorus oxide catalysts were prepared by employing a new strategy, which significantly reduced the complexity of catalyst preparation. The greatly simplified catalyst fabrication benefits a greener and lower-cost process for practical applications. The currently fabricated systems showed ca.

Vanadium Phosphorus Oxide/Siliceous Mesostructured Cellular Foams: efficient and selective for sustainable acrylic acid production via condensation route.

A new type of supported vanadium phosphorus oxide (VPO) with self-phase regulation was simply fabricated (organic solvent free) for the first time by depositing the specific VPO precursor NH(VO)HPO onto the Siliceous Mesostructured Cellular Foams (MCF) with controlled activation. The resulting materials were found to be highly efficient and selective for sustainable acrylic acid (AA) plus methyl acrylate (MA) production via a condensation route between acetic acid (HAc) and formaldehyde (HCHO). A (AA + MA) yield of 83.

Oxidative cyanation of -aryltetrahydroisoquinoline induced by visible light for the synthesis of α-aminonitrile using potassium thiocyanate as a "CN" agent.

A novel method for the synthesis of α-aminonitrile through visible-light-induced oxidative cyanation of -aryltetrahydroisoquinoline with potassium thiocyanate has been developed. The process does not require the use of a photocatalyst, transition metal reagent, strong oxidizing agent, or toxic cyano-containing compound, which makes the reaction simple and green.

Mechanochemically synthesized MgAl layered double hydroxide nanosheets for efficient catalytic removal of carbonyl sulfide and HS.

A solid-state mechanochemical route for rapid synthesis of MgAl layered double hydroxide (LDH) nanosheets large in surface area and decorated with abundant hydroxyl groups was developed for catalytic elimination of carbonyl sulfide and HS, showing activity superior to those of commercial LDHs and porous metal oxides.

Cu-Catalyzed Cross-Dehydrogenative Coupling of Heteroaryl C(sp)-H and Tertiary C(sp)-H Bonds for the Construction of All-Carbon Triaryl Quaternary Centers.

A Cu-catalyzed protocol for cross-dehydrogenative coupling of benzofuranones with quinolines, indoles, carbazoles, and thiophene, which furnishes highly functionalized 3,3-diaryl benzofuranones bearing a three aryl quaternary carbon center at the C3 position in good yields, has been developed. A radical mechanism is proposed.

Organoantimony(III) halide complexes with azastibocine framework as potential antitumor agents: Correlation between cytotoxic activity and N→Sb inter-coordination.

The relationship between chemical structure and in vitro cytotoxic activities of a series of azastibocine-framework organoantimony(III) halide complexes against cancerous (HepG2, MDA-MB-231, MCF-7 and HeLa) and nonmalignant (HEK-293) cell lines was studied for the first time. A positive correlation between cytotoxic activity and the length of N→Sb coordinate bond on azastibocine framework of same nitrogen substituent was observed. By comparison, the organoantimony(III) complex 6-cyclohexyl-12-fluoro-5,6,7,12-tetrahydrodibenzo[c,f][1,5]azastibocine (C4) exhibited the highest selectivity index, giving a IC(nonmalignant)/IC(cancerous) ratio of up to 8.

Establishing the correlation between catalytic performance and N→Sb donor-acceptor interaction: systematic assessment of azastibocine halide derivatives as water tolerant Lewis acids.

A series of organoantimony(iii) halide complexes with a tetrahydrodibenzo[c,f][1,5]azastibocine framework were synthesized and employed as water tolerant Lewis acid catalysts. The results of a systematic structure-activity relationship study demonstrated that the strength of N→Sb donor-acceptor interaction could be synergistically modulated by tuning the properties of the nitrogen substituents and halogen atoms adjacent to the central antimony atom, and consequently resulted in distinct catalytic performances towards organic reactions such as Mannich, cross-condensation, cyclization-aromatization and epoxide aminolysis reaction. The fluorinated organoantimony(iii) derivatives were found to be more active than those of the chlorinated, brominated and iodinated analogues, owing to the use of an Sb-F moiety as a hydrogen bond acceptor.

Carbon-Carbon Bond Formation of Trifluoroacetyl Amides with Grignard Reagents via C(O)-CF Bond Cleavage.

The reaction of trifluoroacetyl amides with Grignard reagent for the substitution of CF group with various alkyl or aryl groups is described. A variety of aryl, quinolin-8-yl, and (hetero)alkyl functional groups as well as F, Cl, and Br atoms are well tolerated. These moisture-stable and easily available trifluoroacetyl amides can be conveniently obtained and used as new versatile precursors for isocyanates.