Supported metals are well-recognized commercial catalysts for important industrial selective hydrogenation. Intrinsic catalysis based on structure-function relationship has traditionally been regarded as a main factor to determine hydrogenation selectivity, while the intense heat release in a strong exothermic reaction also inevitably deteriorates the selectivity by causing coke deposition and/or over-hydrogenation. Herein, this work demonstrates a distribution effect by homogeneously dispersing catalytically-active metal particles on oxide support to enhance the selectivity of exothermic hydrogenation. The catalytically-active metal particles with varied dispersion homogeneity, NiCu here, exhibit similar intrinsic catalysis in the intensely exothermic hydrogenation of alpha-methylstyrene to cumene. However, a distribution effect is found that the increase in metal dispersion homogeneity leads to enhanced cumene selectivity while decreased isopropylcyclohexane (IPCH) selectivity, with a cumene selectivity of > 99 % achieved at a alpha-methylstyrene conversion of > 99 %. The high selectivity is attributed to the in-situ thermal dissipation caused decrease in temperature increment detected at the catalyst bed, while even a slight temperature increase at catalyst bed could be induced by a large temperature rise at catalytic sites. Benefiting from the lowered temperature increment, the over-hydrogenation to IPCH with a higher activation energy has been inhibited.

Topological transformation of layered double hydroxides (LDHs) containing bimetal components is a powerful method for producing bimetal catalysts, but suffers from uncontrollable bimetal structures and catalytically active sites due to the indistinct mechanism. This work demonstrates the manipulation of CuCo structure by simply changing the aspect ratio or Cu/Co distribution (one in layer and the other in interlayer) of LDHs, affording (i) exclusive Janus Cu-Co particles or well-alloyed CuCo particles and (ii) CuCo alloy with Janus Cu-Co, monometallic Co, or monometallic Cu coexisting. The mesoscale key factor in the topological transformation is revealed. In the syngas conversion, the selectivity to alcohol reaches 49.3% and 43.2% with C2+ alcohol fraction of >94% on well-alloyed CuCo and Janus Cu-Co particles with good affinity of Cu-Co sites. But the presence of monometallic Co or Cu suppresses alcohol selectivity or C2+ alcohol fraction by facilitating the production of hydrocarbons or methanol, respectively.

The competition and diversity of coinstantaneous elementary reactions in syngas conversion make the production of targeted products with high selectivity much more challenging. This work demonstrates the control of product distribution in syngas conversion by changing the adsorption strength of non-dissociated CO on engineered Cu sites. The strength of non-dissociated CO adsorption has been tailored by atomic-Cu-1 or ensemble-Cu-n on Co1Ga1 intermetallic compounds. In syngas conversion, the introduction of either Cu sites could promote the selectivity of alcohols, while atomic-Cu-1 sites enhance the production of methanol and ensemble-Cu-n sites favor the production of C2+ alcohol. A strong adsorption of non-dissociated CO occurs on electron-deficient atomic-Cu-1 sites, leading to an increase of alcohols with > 90 % of methanol in alcohols due to direct hydrogenation. A weaker adsorption of non-dissociated CO occurs on ensemble-Cu-n sites, which allows the carbonyl insertion to alkyl species, affording alcohols with similar to 92 % of C2+ alcohol.

Supported Pt as catalysts have been applied for decades in industrial naphtha reforming and light alkane dehydrogenation but suffer from low stability in continuous and frequent regeneration-reaction cycles. In this work, highly stable Pt in the regeneration treatments, achieved by strong interaction with Sn sites confined in the lattice of layered double oxides (LDO), is reported. The dispersion of Pt on as-prepared clusters with lattice-confined Sn reaches 96%, and retains unchanged after the 1st and 2nd oxidation-reduction cycles (periodic calcination in air and reduction in H2). But dramatic decrease in Pt dispersion is observed on clusters with Sn sites outside the lattice of LDO. The high stability of Pt dispersion in regeneration treatments results in almost constant performances in n-heptane reforming at 500 degrees C and propane dehydrogenation at 580 degrees C, between the fresh Pt with lattice-confined Sn catalysts and that after the 1st or 2nd oxidation-reduction cycles.

In a heterogeneous catalytic reaction with strong heat release, the reaction exotherm causes a temperature increment and further has potential effects on product selectivity. This work focuses on syngas conversion, a representative strong exothermic reaction, to reveal a causation effect between the product distribution and the reaction exotherm. Owing to the thermodynamic characteristics that lead to higher heat release for methane or C2+ hydrocarbon formation than that for methanol or C2+ alcohol formation, the decrease in methanol or C2+ alcohol selectivity but increase in methane or C2+ hydrocarbon selectivity could increase the heat release and temperature increment (Delta T). It has been found that the distinguishing activation energies result in different kinetic sensitivities to heat. By decreasing Delta T, carbonyl insertion/C-C coupling reactions are boosted and hydrogenation of dissociated CO is suppressed, affording a significant decrease in methane selectivity and increase in C2+ alcohol and C2+ hydrocarbon selectivity. The activation energy of hydrogenation of nondissociated CO places in the middle among various reactions, leading to an insensitivity of methanol selectivity to the reaction exotherm in this system. The change in product distribution could further aggravate/weaken the heat release, showing a bilateral causality effect between the product distribution and reaction exotherm. Moreover, an optimized model has been developed for correlating the product selectivity (methane, C2+ hydrocarbon, methanol, or C2+ alcohol) with Delta T at a known setting temperature, which well predicts the sensitivity of the reaction exotherm to product distribution. This work innovates an approach to manipulate product distribution in intensely exothermic reactions via thermal management.

Oxidative carbonylation of ethanol to diethyl carbonate (DEC), an essential electrolyte for lithium-ion battery, has attracted broad interest from both academia and industry in recent years. But high selective formation of DEC is a great challenge due to the difficulty in efficient activation of CO at the same time as the site-specific activation of O & horbar;H bond in ethanol. Herein, we propose a Pd-CuxO synergetic catalysis toward oxidative carbonylation of ethanol, where the synergy between Pd and CuxO promotes CO activation and carbonylation, thus increasing the selectivity to the site-specific activation of O & horbar;H bond in ethanol. A nitrogen-doped carbon nanotubes supported Pd-CuxO (Pd-CuxO/NCNTs) has been designed via galvanic displacement of Pd on CuxO to form the strong interactions between Pd and CuxO, affording a selectivity of 94.7% to DEC and a space-time yield (STY) of up to 5966 mgg- 1h- 1, which is an order of magnitude higher than that reported in the literatures. This work offers novel insights for the design of highly efficient catalysts and advances the industrial development for the oxidative carbonylation of ethanol. (c) 2025 The Chemical Industry and Engineering Society of China, and Chemical Industry Press Co., Ltd. All rights are reserved, including those for text and data mining, AI training, and similar technologies.

Photosynthesis is a potential strategy to enable endergonic process that usually needs high-temperature in thermochemistry to supply the energy for inert-bond activation and/or strong endothermic reaction. The conversion of CO2 into value-added C-2-oxygenates is a promising process to realize artificial photosynthesis, but suffers from relatively lower efficiency due to complex multi-electron (>= 10) transfer processes and sluggish kinetics of C-C coupling. This work proposes an all-new H2O-promoted strategy for efficient production of C-2 oxygenates from the concurrent activation and subsequent co-conversion of CO2 with CH4 under photo-thermal cooperation, in which photocatalytic H2O-splitting derived active hydrogen species for CO2 activation, and concomitant active oxygen species for CH4 activation. A formation rate of as high as 2.05 mmol g(-1) h(-1) for C-2-oxygenates (CH3CHO and CH3CH2OH) in a selectivity of > 86% has been afforded over SrTiOx supported CuCo under 200 degrees C and ultraviolet-visible illumination. It has been revealed that SrTiOx drives photocatalytic H2O-splitting under the excitation primary from ultraviolet light, paired Cu-I/Cu-0 sites promote the formation of *CHxO intermediate from CO2, Co sites conduct CH4-to-*CH3, and C-C coupling of *CHxO and *CH3 on adjacent Cu-Co facilitates the generation of C-2-oxygenates. (c) 2024, Dalian Institute of Chemical Physics, Chinese Academy of Sciences. Published by Elsevier B.V. All rights reserved.

Catalytic conversion of biomass-derived 5-(hydroxymethyl)furfural (5-HMF) into carbon-increased hydrocarbons as drop-in energy-rich biofuels has received a great deal of concern for the development of sustainable chemical industry. Here, we demonstrate a one-pot conversion of 5-HMF into C-9-alkanes on one single catalyst, acidic-basic layered double oxides (Mg(Al)(Zr)O) supported CuCo alloy. The well-defined multifunctional catalytic sites with harmonious combination carry out cascade catalysis, affording C-9-alkanes (including 30% of more value-added branched-cycloalkanes) in 83% yield. The basic-acidic sites on Mg(Al)(Zr)O show high activity for aldol condensation of 5-HMF and acetone, producing 4-[5-(hydroxymethyl)-2-furanyl]-3-buten-2-one (HAc) in a yield of >99%. The engineered Co-Cu-Co linkages on supported CuCo perform efficient hydrodeoxygenation, affording C-9-alkanes in a selectivity of 96% from HAc. C-9-cycloalkanes are generated from the cyclization of the corresponding monohydric alcohol intermediates by the synergy of acidic and CuCo sites in the hydrodeoxygenation reaction.

The direct sp3 C–H functionalization of alcohol with N-heterocycles is the most atom-economical pathway to produce hydroxyalkylated N-heterocycles. However, the targeted C–H activation to enable the direct C–C coupling still remains of great challenge due to the concomitant activation of alcoholic O–H. This work puts forward a H-bonding protection for alcoholic O–H for the targeted activation of alcoholic Cα-H bonds. Atomic Fe-N sites anchored in graphitic carbon nitride with uncoordinated nitrogen sites has thus been proposed for this strategy, in which atomic Fe(II)-N sites are supposed to be responsible for the targeted activation of alcoholic Cα-H and the surface uncoordinated nitrogen to for the H-bonding with alcoholic O–H. To demonstrate the strategy, the precise modulation on the atomic Fe-N coordination in the 6-fold cavity from three heptazines have been elaborated. Atomic Fe with four N atoms from two heptazines assisted with the uncoordinated N from the free one heptazine has presented a synergistic H-bonding protection of alcoholic O–H bonds. As a result, the targeted generation and excellent stabilization of hydroxyethyl radicals have been achieved under ambient temperature. The strategy has been successfully applied for 1-propanol, 2-propanol, 1-butanol, and 1-pentanol, thus achieving efficient C–C formation in the hydroxyalkylation of varied N-heterocycles.

Expression of concern for 'Synthesis of a Fe3O4@P4VP@metal-organic framework core-shell structure and studies of its aerobic oxidation reactivity' by Zongcheng Miao et al., RSC Adv., 2017, 7, 2773-2779, https://doi.org/10.1039/C6RA25820D.

Glycerol carbonate, an important glycerol value-added product, has been widely used as the active intermediates and inert solvents in the synthesis of cosmetics, detergents, chemical intermediates, polymers, and so on. The direct carbonylation from glycerol with CO2 is considered as a promising route, but still a tough work due to the thermodynamic stability and the kinetic inertness of CO2. In this work, highly-selective direct carbonylation of glycerol and CO2 into glycerol carbonate has been achieved over highly dispersed MgInCe-mixed metal oxides (MgInCe-MMO), which were prepared through the topological transformation derived from the MgInCe-layered double hydroxides (MgInCe-LDHs). By precisely modulating the surface basic-acidic properties and the oxygen vacancies, an efficient carbonylation of glycerol with CO2 has been achieved with a selectivity of up to > 99% to glycerol carbonate. Deep investigation on the synergistic catalysis of base-acid sites and oxygen vacancies has been clarified.

Carbonylation of ethanol with CO 2 as carbonyl source into value-added esters is of considerable significance and interest, while remains of great challenge due to the harsh conditions for activation of inert CO 2 in that the harsh conditions result in undesired activation of α-C−H and even cleavage of C−C bond in ethanol to deteriorate the specific activation of O−H bond. Herein, we propose a photo-thermal cooperative strategy for carbonylation of ethanol with CO 2 , in which CO 2 is activated to reactive CO via photo-catalysis with the assistance of *H from thermally-catalyzed dissociation of alcoholic O−H bond. To achieve this proposal, an interfacial site and oxygen vacancy both abundant SrTiCuO 3-x supported Cu 2 O (Cu 2 O-SrTiCuO 3-x ) has been designed. A production of up to 320 μmol g −1  h −1 for ethyl formate with a selectivity of 85.6 % to targeted alcoholic O−H activation has been afforded in photo-thermal assisted gas-solid process under 3.29 W cm −1 of UV/Vis light irradiation (144 °C) and 0.2 MPa CO 2 . In the photo-driven activation of CO 2 and following carbonylation, CO 2 activation energy decreases to 12.6 kJ mol −1 , and the cleavage of alcoholic α-C−H bond has been suppressed.

With the widespread use of antibiotics, water pollution and biological systems have become serious. There exist many challenges for their degradation, and the key to photocatalytic degradation is the rational design of photocatalysts and a thorough understanding of their catalytic mechanism. In this paper, tetraphenylphosphorus chloride as a carbon source was doped into g-C3N4, and a C doping g-C3N4 photocatalyst (C-CN-550) was prepared with rich porosity, high surface area, and expanded delocalization of pi-electrons. When ZnCr-LDHs were in situ formed on the C-CN-550 substrate, we constructed an efficient photocatalyst ZnCr-LDHs/C-CN-550 with highly dispersed LDHs, synergy of pi-electrons, defects, interfaces, and fully exposed active sites on the surface. Ciprofloxacin and tetracycline hydrochloride (10 ppm) can be completely degraded within 30 min by the ZnCr-LDHs/C-CN-550 catalyst under visible light irradiation. Further, the synergistic mechanism was revealed through various characterizations, which provides new ideas and strategies for the construction of composite photocatalysts.

Atomically dispersed metal sites afford high activity or selectivity in many heterogeneous catalytic reactions. It is still an open challenge to achieve a high-density dispersion of atomic metals. Herein, this work demonstrates a facile strategy to boost the dispersion density of atomic metals by the induction of meso-stable lattice distortion sites in the topological transformation of layered double hydroxides (LDHs). Meso-stable penta-coordinated Fe-III, resulting from the difference in the thermal stability between Mg-OH and Fe-OH in a LDH lattice, is utilized from MgFe-LDHs as anchoring sites for atomic Pt. The dispersion density of atomic Pt reaches 2.0 Pt-1/nm(2). This strategy in the topological transformation of LDHs has been successfully extended to prepare high-density atomic Ru, Ir, Pd, and Rh. In both catalytic oxidation of HCHO and hydrogenation of furfuryl alcohol, high-density atomic Pt affords high turnover frequency (TOF) by the simultaneous high-efficiency activation of multimolecules on adjacent atomic Pt sites. In HCHO oxidation, high-density atomic Pt affords high mass activity under a high concentration, high space velocity, and low temperature. In furfuryl alcohol hydrogenation, high-density atomic Pt affords high mass activity while retaining >99% selectivity of 2-methylfuran.

高校二级学院办公室是学校内上传下达、协调左右的基层行政管理机构.随着我国高校"双一流"建设的深入推进和"放管服"改革的走深走实,二级学院办公室在高校管理体系中起到了越来越重要的作用.该文通过对高校二级学院办公室新特点、新情况的研究,分析了高校二级学院办公室管理中存在的诸多问题,并有针对性地提出了高校二级学院办公室规范化管理的有效策略.

The application of conventional absorbing materials is limited due to complex preparation process and poor transparency caused by fillers. In this study, a highly transparent ionic organogel was prepared by photocuring a dimethyl sulfoxide (DMSO) solution of a polymerizable magnetic cationic monomer [DAC]5[Dy(NCS)8]. Both components of organogel, which are the photopolymerizable magnetic cationic monomer and polar solvent DMSO, have an important effect on the magnetic losses and dielectric losses properties of the organogel respectively. By tuning the mass ratio of DMSO to the monomer and the content of the cross-linker, the complex permittivity of the gel could be effectively adjusted to improve the impedance matching, and finally a gel with excellent wave absorption properties and good tensile properties was obtained. The optimum organogel was fabricated with a minimum reflection loss of -45.9 dB and a broadest effective absorption bandwidth (EAB) of up to 5.2 GHz, and effective absorption in the millimeter band (26.5-40 GHz) which is within the fifth generation (5G) mobile networks. With the advantages of simple preparation method, arbitrary shape and good adhesion to a variety of substrates and complex surfaces, this multifunctional gel provides a new solution for complex scenarios requiring optical transparency and simultaneous absorption of electromagnetic waves. (c) 2022 The Korean Society of Industrial and Engineering Chemistry. Published by Elsevier B.V. All rights reserved.

实验技术队伍是高校师资队伍的重要组成部分,在人才培养、科学研究、保障实验室安全稳定运行中发挥着关键作用.文章从高校实验技术队伍存在的问题出发,从加强顶层设计、优化考评机制、校院协同培养、完善管理结构等方面,探讨了新时代高校实验技术队伍建设策略,为调动实验技术人员的主观能动性和推进实验教学水平的提升提供了参考思路.

The chemical bond diversity and flexible reactivity of biomass-derived ethanol make it a vital feedstock for the production of value-added chemicals but result in low conversion selectivity. Herein, composite catalysts comprising SiO2-coated single- or multiparticle Au cores hybridized with TiO2 nanoparticles (mono- or multi-Au@SiO2/TiO2, respectively) were fabricated via electrostatic self-assembly. The C-H and O-H bonds of ethanol were selectively activated (by SiO2 and TiO2, respectively) under irradiation to form CH3CH•(OH) or CH3CH2O• radicals, respectively. The formation and depletion kinetics of these radicals was analyzed by electron spin resonance to reveal marked differences between mono- and multi-Au@SiO2/TiO2. Consequently, the selectivity of these catalysts for 1,1-diethoxyethane after 6 h irradiation was determined as 81 and 99%, respectively, which was attributed to the more pronounced effect of localized surface plasmon resonance for multi-Au@SiO2/TiO2. Notably, only acetaldehyde was formed on a Au/TiO2 catalyst without a SiO2 shell. Fourier transform infrared (FTIR) spectroscopy indicated that the C-H adsorption of ethanol was enhanced in the case of multi-Au@SiO2/TiO2, while NH3 temperature-programmed desorption and pyridine adsorption FTIR spectroscopy revealed that multi-Au@SiO2/TiO2 exhibited enhanced surface acidity. Collectively, the results of experimental and theoretical analyses indicated that the adsorption of acetaldehyde on multi-Au@SiO2/TiO2 was stronger than that on Au/TiO2, which resulted in the oxidative coupling of ethanol to afford 1,1-diethoxyethane on the former and the dehydrogenation of ethanol to acetaldehyde on the latter.

Liquid conductor-based flexible sensors with high mechanical deformability and reliable electrical reversibility have aroused great interest in electronic skin, soft robotics, environmental monitoring, and other fields. Herein, we develop a novel strategy to fabricate liquid conductor-based flexible sensors by combining ionic liquid-based magnetofluids (IL-MFs), magnetic printing, and photopolymerization techniques. The as-prepared sensors exhibit excellent electromechanical properties, such as a wide detection range, low hysteresis, fast response time, good durability, etc. Moreover, the gauge factors (GFs) of the sensor could be easily adjusted by changing the modulators with different line widths or patterns, and the strain sensors can also be designed for anisotropic monitoring. Apart from serving as strain sensors, the magnetofluid-based flexible sensors can be used to detect external pressure, human activities, and changes in temperature, illumination, and magnetic field as well. This work provides a facile strategy to fabricate liquid conductor-based multifunctional sensors. Such a magnetofluid-based sensor has a great promising future.

Transformation of ethanol to more valuable C4+ alcohols by coupling reaction has been of great interest from the point of view of chemistry and technology of biomass utilization. This work reports atomic Ru on Mg and Al containing layered double oxides (MgAl-LDO) for ethanol coupling to C4+ alcohols. The atomic Ru remarkably promotes the coupling of ethanol, achieving a selectivity of 82.6% to C4+ alcohols under an ethanol conversion of 29.6%. Through tailoring Ru dispersion and acid-base properties, it has been found that atomic Ru promotes ethanol dehydrogenation and the following aldol condensation of acetaldehyde.