工业催化:选择性提升策略

工业催化直接或间接贡献了世界GDP的20%-30%,推动了产业变革和社会进步.对于工业催化,开发高活性、高选择性和高稳定性的多相催化剂至关重要,而选择性是最主要的挑战.因为实现催化选择性的精确控制是绿色化学的重要概念之一,更是工业催化可持续发展的重要驱动力;而且,选择性不仅决定了催化过程的原子经济性,也影响到后续分离过程的能耗.针对多数工业催化反应存在'活性越高、选择性越低'的相互制约与矛盾问题,本文以若干能源化工催化反应为例,试图总结催化选择性提升的一般策略,以期为有关工业应用的催化新过程提供科学参考.多相催化一般经历与反应物有关的步骤(反应物的外扩散、内扩散和化学吸附)、与反应有关的步骤(活化和表面反应)、以及与产物相关的步骤(产物脱附、内扩散和外扩散).本文依此归纳并举例说明提高选择性的一般策略.在汽油催化吸附脱硫中,主要利用了催化剂中零价镍-氧化锌耦合活性中心的选择吸附策略,使零价镍优先吸附含硫化合物,从而实现选择性脱硫而不饱和烯烃.在甲苯和甲醇侧链烷基化反应中,主要利用了特定空间分布的酸碱吸附位,实现吸附甲苯和稳定甲醛中间体的协同匹配.在乙苯脱乙基型二甲苯异构化反应中,主要利用了双床层对催化剂功能的分离策略,在不同的择形催化剂床层中分别进行乙苯脱乙基反应和二甲苯异构化反应,从而提高对二甲苯的产量.在苯选择加氢制环己烯反应中,主要利用强化产品脱附的策略,促进环己烯产品从亲水改性的催化剂表面脱附,实现环己烯选择性的提升.这些炼油与化工研究案例中同时存在多个连串-平行反应,主要是利用吸附中心、反应中心在时间或空间上的耦合、解耦或限域策略,调控不同途径的扩散能垒、反应能垒,实现了催化剂选择性的提升.多相催化多是复杂过程,基于提高选择性的初步认识,还要结合具体复杂催化过程,系统研究单策略以及多策略组合作用下的选择催化过程,实现在合理时间尺度、空间尺度上设计高选择性的催化剂,而这本质上是一种介尺度催化.     

A hybrid composite of rhenium complexes covalently grafted on reduced graphene oxide/hydrogenated TiO2 as an efficient catalyst for CO2 reduction under visible light

Research on Chemical Intermediates - The photocatalytic conversion of CO2 to fuels by light is of research interest owing to its relevance to environment and energy concerns. In this work, a hybrid...     

Continuous Electrochemical Synthesis of Iso-Coumarin Derivatives from o-(1-Alkynyl) Benzoates under Metal- and Oxidant-Free

A non-oxidant and metal-free strategy for synthesizing iso-coumarin by using a continuous electrochemical microreactor to initiate an oxidative cyclization reaction of o-(1-alkynyl) benzoate and radicals. This efficient and clean continuous electrosynthesis method not only avoids the complicated gas protection operation and production of by-products in the batch processes, but also help to overcome the difficulty that batch metal catalysis and electrocatalysis are difficult to scale up, and has the potential for pilot-scale experiment.     

Effect of the topology on the antibacterial activity of cationic polythioether synthesized by all-click chemistry

Cationic compounds often serve as antibacterial materials for a wide range of applications. However, the relationship of topology−antibacterial activity has been rarely revealed. Herein, three cationic polythioethers (CPTEs) with hyperbranched topologies are well designed and facilely synthesized via an all-click chemistry strategy (including thiol-ene and epoxy-amine additions). These as-prepared CPTEs were found to exhibited outstanding antibacterial activity against Escherichia coli and Staphylococcus aureus with minimum inhibitory concentrations against E. coli of 7.3, 14.6, and 14.6 μg ml⁻¹, and against S. aureus of 14.6, 29.2, and 29.2 μg ml⁻¹, respectively. The antibacterial activity is coincident with their degree of branching (DB, their DB values of 0.81, 0.48, and 0.27), which is mainly attributed to the inherent three-dimensional structure. The present strategy reveals the relationship of polymer topology and antibacterial activity, providing a novel possibility for designing and/or synthesis of high-efficiency antibacterial agents.     

Spleen and thymus metabolomics strategy to explore the immunoregulatory mechanism of total withanolides from the leaves of Datura metel L. on imiquimod-induced psoriatic skin dermatitis in mice

Our previous work demonstrated that total withanolides of Datura metel L. leaves (TWD) exhibited excellent therapeutic effects on psoriasis. However, current knowledge of its mechanisms is incomplete. In this study, integrated spleen and thymus untargeted metabolomics were used to analyze the changes in endogenous metabolites underlying the immunosuppressive activity of TWD on psoriasis animal models induced by imiquimod. The results suggested that TWD treatment markedly attenuated imiquimod-induced psoriasis and showed significant immunosuppressive activity as evidenced by decreased elevation index of spleen and thymus. Meanwhile, TWD significantly reversed the elevation of immunoregulatory factors, including IL-10, IL-17, IL-22 and IL-23. Multivariate trajectory analysis revealed that TWD treatment could restore the psoriasis-disturbed spleen and thymus metabolite profiles towards the normal metabolic status. A total of 25 and 27 metabolites associated with the immunomodulatory effects for which levels changed markedly upon treatment have been identified in spleen and thymus, respectively. These differential metabolites were mainly involved in amino acid metabolism, nucleotide metabolism, fatty acid metabolism and lipid metabolism. Our investigation provided a holistic view of TWD for intervention in psoriasis through immunoregulation and provided further scientific information in vivo about a clinical value of TWD for psoriasis.     

Metal-Free,Visible-Light-Induced Selective C−C Bond Cleavage of Cycloalkanones with Molecular Oxygen

A metal-free, visible-light-induced oxidative C−C bond cleavage of cycloketones with molecular oxygen is described. Cooperative Brønsted-acid catalysis and photocatalysis enabled selective C−C bond cleavage of cycloketones to generate an array of γ-, δ- and ϵ-keto esters under very mild conditions. Mechanistic studies indicate that singlet molecular oxygen (¹O₂) is responsible for this transformation.     

Electrochemical characteristics of the dynamic progression of erosion-corrosion under different flow conditions and their effects on corrosion rate calculation

Journal of Solid State Electrochemistry - The erosion-corrosion performance of X65 carbon steel at different flow conditions was electrochemically studied. Results show that the anodic polarization...     

Polypyrrole modified hierarchical porous CoS2@RGO aerogel electrode for ultrafast sodium storage

Journal of Solid State Electrochemistry - CoS2 nanooctahedrons homogeneously encapsulated by hierarchical porous-reduced graphene oxide and polypyrrole thin film are constructed via a simple...