One-Pot Green Synthesis of 1, 4-Dihydropyridine Derivatives Using Polyindole TiO2 Nanocatalyst by Solvent Free Method

This study used a Polyindole in combination with TiO2 nanocatalyst as an efficient heterogeneous catalyst to carry out a multi-component Hantzsch reaction involving different aromatic aldehydes with methyl acetoacetate, and aqueous ammonium to create 1,4-dihydropyridine derivatives under solvent free condition at ambient temperature. A broad range of aldehydes and methyl acetoacetates, ranging from heteroaromatic to polyaromatic one, with high level of functional group tolerance can be used to provide the desired products possessing relevant medicinal moiety in high yields. This technology has prospective advantages over current protocols, including the utilization of a cheap, stable, recyclable, and safe catalyst, quicker reaction times with higher yields and simple product isolation.

Ru-Cu/Fe_3O_4-TiO_2催化剂上甘油氢解制备1,2-丙二醇的研究

以生物柴油生产过程中副产的甘油为原料,通过催化氢解制备1,2-丙二醇是增长生物柴油产业链、提高其经济效益的有效途径.采用浸渍法制备了双金属磁性催化剂Ru-Cu/ Fe3 O4 -TiO2 ,利用X 射线衍射、X 射线光电子能谱、透射电子显微镜、N2 吸附等方法对催化剂进行了表征,考察了Ru/ Cu 摩尔比、反应温度、H2 压力、反应时间和催化剂用量等因素对催化剂性能的影响.结果表明,Ru-Cu/ Fe3 O4 -TiO2 双金属催化剂具有很高的催化活性和良好的1,2-丙二醇选择性.Cu 的加入没有明显改变Ru 的化学环境,但有效地提高了1,2-丙二醇的选择性,同时Ru 可改善Cu 在钛铁复合载体上的分散性,从而获得了平均金属粒径在5-9 nm 左右的催化剂.在Ru/ Cu 摩尔比1 ∶1. 6、反应温度200 ℃、H2 压力4. 0 MPa、反应时间10 h 的条件下,甘油转化率和1,2-丙二醇的选择性分别高达96. 12% 和86. 77%.反应后产物与催化剂可有效实现磁性分离,为该过程的工业化应用奠定了基础.

Effects of Co_3O_4 nanocatalyst morphology on CO oxidation:Synthesis process map and catalytic activity

This study focuses on drawing a hydrothermal synthesis process map for Co3O4 nanoparticles with various morphologies and investigating the effects of Co3O4 nanocatalyst morphology on CO oxidation.A series of cobalt-hydroxide-carbonate nanoparticles with various morphologies（i.e.,nanorods,nanosheets,and nanocubes） were successfully synthesized,and Co3O4 nanoparticles were obtained by thermal decomposition of the cobalt-hydroxide-carbonate precursors.The results suggest that the cobalt source is a key factor for controlling the morphology of cobalt-hydroxide-carbonate at relatively low hydrothermal temperatures（≤ 140℃）.Nanorods can be synthesized in CoCl2 solution,while Co（NO3）2 solution promotes the formation of nanosheets.Further increasing the synthesis temperature（higher than 140 ℃） results in the formation of nanocubes in either Co（NO3）2 or CoCl2 solution.The reaction time only affects the size of the obtained nanoparticles.The presence of CTAB could improve the uniformity and dispersion of particles.Co3O4 nanosheets showed much higher catalytic activity for CO oxidation than nanorods and nanocubes because it has more abundant Co^（3＋） on the surface,much higher reducibility,and better oxygen desorption capacity.

SMFs-supported Pd nanocatalysts in selective acetylene hydrogenation:Pore structure-dependent deactivation mechanism

In the present study,CNFs,ZnO and Al2O3 were deposited on the SMFs panels to investigate the deactivation mechanism of Pd-based catalysts in selective acetylene hydrogenation reaction.The examined supports were characterized by SEM,NH3-TPD and N2adsorption-desorption isotherms to indicate their intrinsic characteristics.Furthermore,in order to understand the mechanism of deactivation,the resulted green oil was characterized using FTIR and SIM DIS.FTIR results confirmed the presence of more unsaturated constituents and then,more branched hydrocarbons formed upon the reaction over alumina-supported catalyst in comparison with the ones supported on CNFs and ZnO,which in turn,could block the pores mouths.Besides the limited hydrogen transfer,N2 adsorption-desorption isotherms results supported that the lowest pore diameters of Al2O3/SMFs close to the surface led to fast deactivation,compared with the other catalysts,especially at higher temperatures.

In situ preparation of well-dispersed CuO nanocatalysts in heavy oil for catalytic aquathermolysis

We developed an in situ synthesis strategy for preparing well-dispersed CuO nanoparticles as aquathermolysis catalyst for viscosity reduction in Shengli heavy oil(China). A Cu(OH)_2-contained microemulsion was employed as a carrier to disperse the precursor Cu(OH)_2 to the heavy oil phase. Under aquathermolysis condition(240 ℃, 2.5 MPa of N_2), the Cu(OH)_2 precursors would first be converted in situ to well-crystallized and size-homogeneous CuO nanoparticles naturally, catalyzed by which the viscosity of Shengli heavy oil could be reduced as much as 94.6%; simultaneously, 22.4% of asphaltenes were converted to light components. The agglomeration of the in situ prepared monoclinic CuO nanoparticles could be negligible throughout the catalytic reaction. Based on the characterization results of ~1 H NMR, elemental analysis and GC-MS of oil samples before and after catalytic aquathermolysis, the mechanism for viscosity reduction of heavy oil in the catalytic system was investigated.

Catalytic Performance of CeO_2/ZnO Nanocatalysts on the Oxidative Coupling of Methane with Carbon Dioxide and their Fractal Features

CeO2/ZnO nanocatalysts were prepared from the coupling route of homogeneous precipita-tion with microemulsion and the impregnation method. The catalytic performance of these two kinds of catalysts on the oxidative coupling of methane with carbon dioxide was tested and compared; the frac-tal behavior of the nanocatalysts was analyzed using fractal theory. The CeO2/ZnO nanocatalysts had much higher activity than the catalysts prepared by impregnation method. There was no regular relation-ship between the average size of CeO2/ZnO nanocatalysts and their catalytic performance; however, the conversion of methane increased with the increase of the fractal dimension of CeO2/ZnO nanocatalysts.

Red Blood Cell-Mimic Nanocatalyst Triggering Radical Storm to Augment Cancer Immunotherapy

Red blood cells(RBCs)have recently emerged as promosing candidates for cancer treatment in terms of relieving tumor hypoxia and inducing oxidative damage against cancer cells,but they are still far from satisfactory due to their limited oxygen transport and reactive oxygen species generation rate in tumor tissue.Herein,artificial RBCs(designated FTP@RBCM)with radical storm production ability were developed for oncotherapy through multidimensional reactivity pathways of Fe-protoporphyrin-based hybrid metal-organic frameworks(FTPs,as the core),including photodynamic/chemodynamic-like,catalase-like and glutathione peroxidase-like activities.Meanwhile,owing to the advantages of long circulation abilities of RBCs provided by their cell membranes(RBCMs),FTP with a surface coated with RBCMs(FTP@RBCM)could enormously accumulate at tumor site to achieve remarkably enhanced therapeutic efficiency.Intriguingly,this ROS-mediated dynamic therapy was demonstrated to induce acute local inflammation and high immunogenic cancer death,which evoked a systemic antitumor immune response when combined with the newly identified T cell immunoglobulin and mucin-containing molecule 3(Tim-3)checkpoint blockade,leading to not only effective elimination of primary tumors but also an abscopal effect of growth suppression of distant tumors.Therefore,such RBC-mimic nanocatalysts with multidimensional catalytic capacities might provide a promising new insight into synergistic cancer treatment.

Silicalite-1 zeolite encapsulated Fe nanocatalyst for Fenton-like degradation of methylene blue

Encapsulation of Fe nanoparticles in zeolite is a promising way to significantly improve the catalytic activity and stability of Fe-based catalysts during the degradation process of organic pollutants.Herein,Fe nanocatalysts were encapsulated into silicalite-1(S-1)zeolite by using a ligand-protected method(with dicyandiamide(DCD)as a organic ligand)under direct hydrothermal synthesis condition.High-resolution transmission electron microscopy(HRTEM)results confirmed the high dispersion of Fe nanocatalysts which were successfully encapsulated within the voids among the primary particles of the S-1 zeolite.The developed S-1 zeolite encapsulated Fe nanocatalyst(Fe@S-1)exhibited significantly improved catalytic activity and reusability in the catalytic degradation process of methylene blue(MB).Specifically,the developed Fe0.021@S-1 catalyst showed high catalytic degradation activity,giving a high MB degradation efficiency of 100%in 30 min,outperformed the conventional impregnated catalyst(Fe/S-1).Moreover,the Fe@S-1 catalyst afforded an outstanding stability,showing only ca.7.9%activity loss after five cycling tests,while the Fe/S-1 catalyst presented a significantly activity loss of 50.9%after only three cycles.Notably,the encapsulation strategy enabled a relatively lower Fe loading in the Fe@S-1 catalyst in comparison with that of the Fe/S-1 catalyst,i.e.,0.35%vs.0.81%(mass).Radical scavenging experiments along with electron spin resonance(ESR)measurements confirmed that the major role of
OH in the MB degradation process.Specifically,Fe@S-1 catalyst with high molar ratio of[Fe(DCD)]Cl3 is beneficial to form Fe complexes/nanoclusters in the voids(which has large pore size of 1–2 nm)among the primary particles of the zeolite,and thus improving the diffusion and accessibility of reactants to Fe active sites,and thus exhibiting a relatively higher degradation efficiency.This work demonstrates that zeolite-encapsulated Fe nanocatalysts present potential applications in the advanced oxidation of wastewater treatment.

Oxidative Coupling of Methane over Li/MgO： Catalyst and Nanocatalyst Performance

The Li/MgO catalyst and nanocatalyst were prepared by the incipient wetness impregnation and sol-gel method, respectively. The catalytic performance of the Li/MgO catalyst and nanocatalyst on oxidative coupling of methane was compared. The catalysts prepared in two ways were characterized by X-ray powder diffraction, Brunauer-Emmett-Teller surface and transmission electron microscope. The catalyst was tested at temperature of 973-1073 K with constant total pressure of 101 kPa. Experimental results showed that Li/MgO nanocatalyst in the oxidative coupling of methane would result in higher conversion of methane, higher selectivity, and higher yield of main products （ethane and ethylene） compared to ordinary catalyst. The results show the improved influence of nanoscale Li/MgO catalyst performance on oxidative coupling of methane.

Kinetic studies on extra heavy crude oil upgrading using nanocatalysts by applying CFD techniques

Regarding the growth of global energy consumption and the paucity of light crude oil, extracting and using heavy and extra heavy crude oil has received much more attention, but the application of this kind of oil is complicated due to its very high molecular weight. High viscosity and low flowability complicate the transportation of heavy and extra heavy crude oil. Accordingly, it is essential to reduce the viscosity of heavy and extra heavy crude oil through in-situ operations or immediate actions after extraction to reduce costs. Numerical simulations are influential methods, because they reduce calculation time and costs. In this study, the cracking of extra heavy crude oil using computational fluid dynamics is simulated, and a unique kinetic model is proposed based on experimental procedures to predict the behavior of extra heavy crude oil cracking reaction. Moreover, the hydrodynamics and heat transfer of the system and influence of nanocatalysts and temperature on the upgrading of crude oil are studied. The geometry of a reactor is produced using commercial software, and some experiments are performed to examine the validity and accuracy of the numerical results. The findings reveal that there is a good agreement between the numerical and experimental results. Furthermore, to investigate the main factors affecting the process, sensitivity analysis is adopted. Results show that type of catalyst and concentration of catalyst are the parameters that influence the viscosity reduction of extra heavy crude oil the most. The findings further revealed that when using a 25 nm SiO_2 nanocatalyst, a maximum viscosity reduction of 98.67% is observed at 623 K. Also, a catalyst concentration of 2.28 wt% is best for upgrading extra heavy crude oil. The results obtained through sensitivity analysis, simulation model, and experiments represent effectual information for the design and development of high performance upgrading processes for energy applications.

A simple kinetic model for oxidative coupling of methane over La_(0.6)Sr_(0.4)Co_(0.8)Fe_(0.2)O_(3-δ) nanocatalyst

A simplified kinetic model for the oxidative coupling of methane over a La0.6Sr0.4Co0.8Fe0.2O3-δ nanocatalyst is presented. The kinetic model was developed by experimental data in a catalytic micro-reactor covering a wide range of reaction conditions （0.04〈PO2〈0.15 atm, 0.2〈PCH4〈0.85 atm, 800〈T 〈900 °C）. Power law rate expressions were used for all reactions. The reaction scheme proposed in this work includes the most important reactions of oxidative coupling of methane and those involved in most of the available mechanisms in the literature. From the experimental data, kinetic parameters, i.e., pre-exponential factors, activation energies and power law exponents, were estimated. The compatibility of model results with experimental data was investigated and the accuracy of the model prediction was evaluated. Rates of methane consumption, C2＋ and COx formation, methane conversion, and C2＋ selectivity and yield were compared with experimental data using presented kinetics. The kinetic model was also compared with four previous kinetic models in terms of methane conversion.

In situ XRD Studies on Heat-treated PtRu/C Nanocatalysts

Extremely small PtRu/C nanocatalysts were prepared via a carbonyl route. A thorough in situ reduction X-ray structural characterization of these catalysts was performed. After synthesis and storage under ambient condi- tions, the diffraction patterns of PtRu/C catalysts were seriously modified, indicating the surface oxide formation. In the reduced state, the particle size is around 2 nm. The observed relative fluctuations of lattice constants are 3%, which is far too large to be explained by a compositional fluctuation. Their origin is attributed to strong but isotropic strains and is related to the alloy formation. The annealing experiments show all the catalysts present an exceptional thermal stability when annealed in inert ambient, especially that of the Pt1Ru1/C catalyst. Besides, it is interesting to note that there is no thermal expansion evidence from the patterns.

Improving plasma sterilization by constructing a plasma photocatalytic system with a needle array corona discharge and Au plasmonic nanocatalyst

Efficient sterilization by a plasma photocatalytic system(PPS)requires strong synergy between plasma and photocatalyst to inactivate microorganisms while suppressing the formation of secondary pollutants.Here,we report that a PPS constructed from a needle array corona discharge and Au/TiO2plasmonic nanocatalyst could remarkably improve the sterilization of Escherichia coli(E.coli)and alleviate formation of the discharge pollutant O3.At 6 kV,the combination of corona discharge and Au/TiO2achieves sterilization efficiency of 100%within an exposure time of 5 min.At 5 kV and an exposure time of 8 min,the presence of Au/TiO2improves sterilization efficiency of the corona discharge from 73%to 91%and reduces the O3concentration from 0.38 to 0.04 ppm,whereas the presence of TiO2reduces the sterilization efficiency and O3concentration to 66%and 0.17 ppm,respectively.The Au/TiO2in the PPS enables a uniform corona discharge,enhances the interaction between plasma,E.coli and nanocatalysts,and suppresses the formation of O3.Further,the Au/TiO2can be excited by ultraviolet-visible light emitted from the plasma to generate electron-hole pairs,and thus contributes to the formation of reactive radicals and the oxidative inactivation of E.coli.The PPS constructed from a needle array corona discharge and Au-based plasmonic nanocatalyst provides a promising approach for developing high-efficiency sterilization techniques.

Crystal facet engineering coexposed CuIn(200)and In(101)in CuIn alloy nanocatalysts enabling selective and stable CO_(2)electroreduction

The electrocatalytic carbon dioxide reduction reaction(eCO_(2)RR)into high-value-added chemicals and fuels is a promising strategy to mitigate global warming.However,it remains a significant stumbling block to the rationally tuning lattice plane of the catalyst with high activity to produce the target product in the eCO_(2)RR process.To attempt to solve this problem,the Culn bimetallic alloy nanocatalyst with specifically exposed lattice planes is modulated and electrodeposited on the nitrogen-doped porous carbon cloth by a simple two-step electrodeposition method,which induces high Faraday efficiency of 80%towards HCOO-(FEHCOO-)with a partial current density of 13.84 mA cm-2at-1.05 V(vs.RHE).Systematic characterizations and theoretical modeling reveal that the specific coexposed Culn(200)and In(101)lattice facets selectively adsorbed the key intermediate of OCHO*,reducing the overpotential of HCOOH and boosting the FEHCOO-in a wide potential window(-0.65--1.25 V).Moreover,a homogeneous distribution of Culn nanoparticles with an average diameter of merely~3.19 nm affords exposure to abundant active sites,meanwhile prohibiting detachment and agglomeration of nanoparticles during eCO_(2)RR for enhanced stability attributing to the self-assembly electrode strategy.This study highlights the synergistic effect between catalytic activity and facet effect,which opens a new route in surface engineering to tune their electrocatalytic performance.

Graphene derivatives supported nanocatalysts for oxygen reduction reaction

Very recent progress on the graphene derivatives supported variable nanocatalysts for oxygen reduction reaction （ORR） in fuel cell is reviewed. First, common electrochemical techniques to characterize graphene-based electrocatalysts are mentioned. Second, recent updates on gra- phene-derived electrocatalysts are introduced. In this part, both electrochemical activity and stabil- ity of Pt catalysts can be improved when they are supported by reduced graphene oxide （RGO）. Other noble-metal catalysts including Pd, Au, and Ag showing comparable performance have been investigated. The stability of Pd catalyst is enhanced by RGO or few-layered graphene support. Syn- thetic approaches for Au or Ag catalysts supported on graphene oxide are discussed. In addition, non-noble transition metals in N4-chelate complexes can reduce oxygen electrochemically. Fe and Co are cheap alternative catalysts for ORR. In most cases, the stability and tolerance issues are overcome well, but their overall performances don＇t seem to surpass Pt/C catalyst yet,

AuAg合金纳米催化剂的制备及应用研究进展

目的纳米Au催化剂一直是多相催化领域的典型研究材料之一,其具有特殊的电子、结构性质及对诸多氧化、还原反应历程的高催化性能。但是纳米Au催化剂存在尺寸依赖性强,对O_(2)等基础物质活化能力弱等问题。Ag与Au形成合金材料则是解决上述问题的重要途径之一。已有研究中采用多种不同的AuAg催化剂制备方法,并且其在不同催化应用中涉及多种催化机理,但未有研究将其制备过程以及协同催化机理进行对比总结。因此,针对AuAg合金催化剂,综述了其常见的制备方法和预处理条件及其在CO氧化等氧化反应、不饱和醛加氢等加氢反应中的应用以及催化反应机制,并提出了未来可能的发展方向。方法通过对AuAg催化剂的研究和应用进行综述,分析了不同制备方法的特点及预处理条件对AuAg催化剂结构的影响以及AuAg催化剂在不同反应中的催化机理。结果在该合金材料的制备和预处理方面,对比了不同制备方法及其对该合金颗粒在载体表面负载状况的影响机制,也深入探讨了预处理条件对AuAg纳米粒子的尺寸及合金化程度的调控作用。在催化应用上,Ag的加入能够改善纳米Au的抗烧结能力,二者间的电子效应也可提升材料对O_(2)等基础物质活化能力,并降低Au颗粒尺寸变化对催化反应结果的影响,最终高效催化CO氧化、醇氧化、不饱和醛加氢、炔烃加氢以及硝基芳香化合物还原等反应历程。结论目前有多种制备AuAg合金纳米催化剂的方法,而其结构的可控及稳定的合成仍是未来的研究重点。同时,AuAg催化剂在不同反应中催化机理的探索对AuAg催化剂的定向设计尤为重要,应进行更深入的研究,以更快实现工业应用。

光电催化耦合生物电化学技术去除VOCs研究进展

通过研发和应用高活性单原子催化剂,整合生物电化学和光电催化作用,光电催化耦合生物电化学技术实现了气-液一体化和高效低碳的VOCs净化处理。本文综述了光电催化、微生物燃料电池产电驱动阴极光电耦合催化去除VOCs,以及复合亚纳米高效催化剂研发方面的创新成果,对光电催化与生物电化学联合治理VOCs的技术优势、应用前景以及所面临的机遇和挑战进行了深入探讨。

晶相设计钌基纳米催化剂提高CO_(2)甲烷化活性

金属纳米颗粒在许多化学反应中表现出优异的催化性能,因而广泛用于能源和环境等催化领域.形貌是影响其催化行为的关键因素之一,它通过改变金属纳米颗粒表层原子排列结构,进而调控化学反应过程中的物质吸附、催化机理和反应动力学.此外,由于金属存在多种晶相结构,其纳米颗粒暴露的表面结构也可通过改变晶相得以实现.该调控策略可使得纳米颗粒具有独特的表面结构,并展现出不同的催化性能.因此,金属纳米颗粒的晶相设计为优化金属催化剂的催化性能提供了一种有效方式.Ru基纳米催化剂对CO_(2)甲烷化反应具有较好的活性和选择性,且密堆积的Ru(0001)晶面被证明是hcp相Ru纳米催化剂的活性中心,而(10-11)面对CO_(2)甲烷化反应的贡献较小.因此,开发具有更丰富密堆积fcc-(111)表面的Ru基纳米催化剂,有望大幅提高CO_(2)甲烷化的活性.本文首先通过密度泛函理论计算和微观动力学模拟,研究了fcc相Ru纳米催化剂的密堆积(111)晶面上CO_(2)加氢反应的催化机理.结果表明,与hcp-(0001)相比,该密堆积的fcc-(111)表面因能促进CO_(2)的吸附活化,而具有更好的CO_(2)甲烷化反应活性.制备了具有完全暴露fcc-(111)晶面的二十面体Ru金属纳米颗粒,并将其负载于惰性载体氧化铝上,结果表明,CO_(2)甲烷化活性比传统六方密堆积相(hcp)的钌基催化剂高5‒8倍,证实了fcc相催化剂具有更高的甲烷化催化性能.同时,在较高的反应温度下,fcc-晶相的Ru基催化剂在初始反应阶段甲烷化反应活性逐渐下降,但其CO_(2)甲烷化活性仍远高于hcp-相催化剂.原位X射线衍射和环境透射电镜等结果表明,在反应温度高于250°C条件下,fcc-晶相的金属催化剂发生部分晶相转变.该相变主要发生于Ru金属纳米颗粒的聚集体,并伴随着金属粒子的团聚和粒径的增长;然而,单颗粒分散的Ru纳米粒子在相同条件下仍能维持其fcc-晶相,从而确保了其较高的甲烷化活性.此外,原位红外结果进一步证实了CO_(2)甲烷化在Ru基纳米催化剂上通过氢化生成HCOO*中间体的反应路径,以及Ru纳米颗粒在反应过程中的动态结构演化.综上,金属纳米颗粒的晶相设计是调控表面原子结构及其催化反应性能的有效手段.通过对Ru基纳米催化剂的晶相设计,可以显著提升其在CO_(2)甲烷化反应中的催化活性.然而,潜在的高温晶相转变可导致催化剂活性的部分失活.总之,晶相设计通过对金属纳米粒子表面原子结构的调变,为高效催化剂的设计开发和反应机理的深入研究提供了新的机遇.