丁二烯定向合成C6高值化学品高效均相与多相催化体系构建

中国科学院兰州化学物理研究所、杭州师范大学与中海油北京材料院研究团队利用“异构体配体空间取向调控”策略,构建了适配直链中间产物过渡态的“催化口袋”,建立了丁二烯双氢氰化一步合成二腈高效催化新体系.

A review of the direct oxidation of methane to methanol

This article briefly reviewed the advances in the process of the direct oxidation of methane to methanol （DMTM） with both heterogeneous and homogeneous oxidation. Attention was paid to the conversion of methane by the heterogeneous oxidation process with various transition metal ox‐ides. The most widely studied catalysts are based on molybdenum and iron. For the homogeneous gas phase oxidation, several process control parameters were discussed. Reactor design has the most crucial role in determining its commercialization. Compared to the above two systems, aque‐ous homogenous oxidation is an efficient route to get a higher yield of methanol. However, the cor‐rosive medium in this method and its serious environmental pollution hinder its widespread use. The key challenge to the industrial application is to find a green medium and highly efficient cata‐lysts.

Iron-glutamate-silicotungstate ternary complex as highly active heterogeneous Fenton-like catalyst for 4-chlorophenol degradation

A novel iron-glutamate-silicotungstate ternary complex（FeШGluS iW） was synthesized from ferric chloride（FeI II）,glutamic acid（Glu）,and silicotungstic acid（SiW）,and used as a heterogeneous Fenton-like catalyst for 4-chlorophenol（4-CP） degradation at neutral pH value. The prepared FeШGluS iW was characterized using inductively coupled plasma atomic emission spectroscopy,thermogravimetry,Fourier-transform infrared spectroscopy,ultraviolet-visible diffuse reflectance spectroscopy,X-ray diffraction,and field-emission scanning electron microscopy. The results showed that FeШGluS iW has the formula [Fe（C5H8NO4）（H2O）]2SiW 12O40？13H2O,with glutamate moiety and Keggin-structured SiW 12O404- heteropolyanion. The catalyst showed high catalytic activity in 4-CP degradation in the dark and under irradiation. Under the conditions of 4-CP 100 mg/L,FeШGluS iW 1.0 g/L,H2O2 20 mmol/L,and pH = 6.5,4-CP was completely decomposed in 40 min in the dark and in 15 min under irradiation. When the reaction time was prolonged to 2 h,the corresponding total organic carbon removals under dark and irradiated conditions were ca. 27% and 72%,respectively. The high catalytic activity of FeI IIGluS iW is resulted from hydrogen bonding of H2O2 on the FeI IIGluS iW surface. The enhanced degradation of 4-CP under irradiation arises from simultaneous oxidation of 4-CP through Fenton-like and photocatalytic processes respectively catalyzed by ferric iron and the SiW 12O404- hetropolyanion in FeШGluS iW.

Single-atom catalysis: Bridging the homo-and heterogeneous catalysis

Single-atom catalysis,the catalysis by single-atom catalysts(SACs),has attracted considerable attention in recent years as a new frontier in the heterogeneous catalysis field.SACs have the advantages of both homogeneous catalysts(isolated active sites)and heterogeneous catalysts(stable and easy to separate),and are thus predicted to be able to bridge the homo-and heterogeneous catalysis.This prediction was first experimentally demonstrated in 2016.In this mini-review,we summarize the few homogeneous catalysis progresses reported recently where SACs have exhibited promising application:a)Rh/ZnO and Rh/CoO SAC have been used successfully in hydroformylation of olefin of which the activity are comparable to the homogeneous Wilkinson’s catalyst;b)a Pt/Al2O3 SAC has shown excellent performance in hydrosilylation reaction;and c)M-N-C SACs(M=Fe,Co etc.)have been applied in the activation of C–H bonds.All of these examples suggest that fabrication of suitable SACs could provide a new avenue for the heterogenization of homogeneous catalysts.These pioneering works shed new light on the recognition of single-atom catalysis in bridging the homo-and heterogeneous catalysis.

可溶性多孔高分子的合成及应用研究进展

综述将着重介绍可溶性多孔高分子的合成策略及应用方面的最新研究进展。从扭曲构象单体构筑法、超支化聚合法以及限域空间聚合法等三方面对可溶性多孔高分子的合成研究进展进行了归纳,并总结可溶性多孔高分子在气体分离、多相催化新策略、能源等方面的最新应用进展。不断丰富可溶性多孔高分子材料的结构多样性、发展新颖聚合方法并拓展其新应用领域,是该领域的研究热点。

Pd embedded in porous carbon （Pd@CMK-3） as an active catalyst for Suzuki reactions： Accelerating mass transfer to enhance the reaction rate

Heterogeneous catalysts are promising candidates for use in organic reactions due to their advantages in separation, recovery, and environment compatibility. In this work, an active porous catalyst denoted as Pd embedded in porous carbon （Pd@CMK-3） has been prepared by a strategy involving immersion, ammonia- hydrolysis, and heating procedures. Detailed characterization of the catalyst revealed that Pd（0） and Pd（I1） species co-exist and were embedded in the matrix of the porous carbon （CMK-3）. The as-prepared catalyst has shown high activity toward Suzuki reactions. Importantly, if the reaction mixture was homogenized by two minutes of ultrasonication rather than magnetic stirring before heating, the resistance to mass transfer in the pore channels was significantly reduced. As a result, the reactions proceeded more rapidly and a four-fold increase in the turnover frequency （TOF） could be obtained. When the ultrasonication was employed throughout the entire reaction process, the conversion could also exceed 90% even without the protection of inert gas, and although the reaction temperature was lowered to 30 ℃. This work provides a method for fabricating highly active porous carbon encapsulated Pd catalysts for Suzuki reactions and proves that the problem of mass transfer in porous catalysts can be conveniently resolved by ultrasonication without any chemical modification being necessary.

Microporous polymer based on hexaazatriphenylene-fused triptycene for CO2 capture and conversion

Chemical conversion of carbon dioxide(CO2)to value-added useful chemicals like cyclic carbonates represents one potential solution to climate warming.Here,a kind of porous organic polymer(HAT-TP)with large surface area and excellent carbon dioxide uptake capacity is prepared via a condensation reaction to introduce hexaazatriphenylene(HAT)units into triptycene(TP)-based microporous polymer.HAT-TP can coordinate with zinc ions,and the resulting polymer(Zn/HAT-TP)can be utilized as an efficient recyclable catalyst for chemical conversion of CO2 into cyclic carbonates with epoxides.