采用浸渍-还原法在炭纤维表面制备纳米镍催化剂颗粒

为了在炭纤维表面原位生长纳米炭纤维/纳米碳管,研究它对炭/炭复合材料微观界面结构和导热性能的影响,以硝酸镍为催化剂前驱体,H2为还原气体,N2为载气,采用浸渍-还原技术在炭纤维表面制备纳米Ni催化剂颗粒。用扫描电镜观察Ni颗粒形貌和粒径,分析讨论还原温度和时间对纳米Ni颗粒的影响及纳米颗粒的形成原因。研究结果表明:随着还原温度升高,Ni颗粒逐渐变大;随着还原时间增加,催化剂前驱体涂层先分裂,再逐渐形成纳米Ni颗粒,而后又因烧结变大;H2和N2气在Ni颗粒形成过程中还起到刻蚀涂层、吸附弱化颗粒间粘结力的作用;合成纳米Ni颗粒的最佳工艺条件是:还原温度为400～450℃,还原时间为30～60min。

铁单原子及碳化铁复合催化剂的制备及电催化应用

采用球磨-煅烧方法,一次制备出铁单原子-纳米颗粒混合催化剂和钌-铁双金属电催化剂(Ru-Fe DMCs)两种不同类型的催化剂。这两种低成本且容易制备的催化剂尤其是铁单原子-纳米颗粒混合催化剂在碱性溶液中表现出了优异的析氧反应(OER)性能,在10和50 mA/cm^(2)的电流密度下具有275 mV和403 mV的低过电位,经过12 h的稳定性实验,其OER催化性能未见明显改变。针对铁单原子-纳米颗粒混合催化剂重点分析了其结构以及元素价态和组成,研究表明铁单原子-纳米颗粒混合催化剂是一种呈现多孔层碳纳米片状的铁单原子与铁纳米颗粒共存的混合催化剂,能显著提高电化学析氧反应的性能及稳定性。

低压化学气相沉积法制备单壁碳纳米管

采用低压化学气相沉积(CVD)技术在MgO载体中的Fe、Co等纳米催化颗粒上制备碳纳米管(CNTs),用高分辨透射电子显微镜(HRTEM)及喇曼光谱仪(Raman)对生长的CNTs结构特性进行了分析研究,结果表明制备的样品中虽含多壁碳纳米管,但单壁碳纳米管(SWNTs)居多,直径约为0.6～2nm,分布均匀,且既包含金属型管,也包含半导体型管。低压MgO载体CVD制备技术,大大增加了等量Fe、Co等催化反应颗粒的比表面积和反应活性,制备的单壁管产额大、成本低、CNTs更易于提纯。

Poly(ethylenimine)-assisted synthesis of hollow carbon spheres comprising multi-sized Ni species for CO_(2) electroreduction

Electrochemical CO_(2) reduction to produce value-added chemicals and fuels is one of the research hotspots in the field of energy conversion.The development of efficient catalysts with high conductivity and readily accessible active sites for CO_(2) electroreduction remains challenging yet indispensable.In this work,a reliable poly(ethyleneimine)(PEI)-assisted strategy is developed to prepare a hollow carbon nanocomposite comprising a single-site Ni-modified carbon shell and confined Ni nanoparticles(NPs)(denoted as Ni@NHCS),where PEI not only functions as a mediator to induce the highly dispersed growth of Ni NPs within hollow carbon spheres,but also as a nitrogen precursor to construct highly active atomically-dispersed Ni-Nx sites.Benefiting from the unique structural properties of Ni@NHCS,the aggregation and exposure of Ni NPs can be effectively prevented,while the accessibility of abundant catalytically active Ni-Nx sites can be ensured.As a result,Ni@NHCS exhibits a high CO partial current density of 26.9 mA cm^(-2) and a Faradaic efficiency of 93.0% at-1.0 V vs.RHE,outperforming those of its PEI-free analog.Apart from the excellent activity and selectivity,the shell confinement effect of the hollow carbon sphere endows this catalyst with long-term stability.The findings here are anticipated to help understand the structure-activity relationship in Ni-based carbon catalyst systems for electrocatalytic CO_(2) reduction.Furthermore,the PEI-assisted synthetic concept is potentially applicable to the preparation of high-performance metal-based nanoconfined materials tailored for diverse energy conversion applications and beyond.

醇的选择性催化氧化研究进展

本文从均相催化、多相催化、光催化氧化及其纳米颗粒催化等角度阐述醇选择氧化到醛酮的进展。重点介绍了以过渡金属为催化剂的催化氧化体系,并概述近年来光催化及纳米颗粒催化在醇的氧化中的应用。绿色化学的兴起,使未来新能源、新材料的开发与应用具有广阔的前景。

负载纳米钯颗粒在邻位导向磺化反应中的催化特性探究

报道了一种负载钯纳米颗粒催化2-苯基吡啶与芳磺酰氯的邻位导向磺化反应.对反应前后的负载钯纳米颗粒催化剂进行X射线光电子能谱(XPS)分析,发现反应后钯完全被氧化.结果证明钯催化的邻位导向磺化反应是经由PdII/IV催化循环,而不是Pd0/II催化循环.热过滤实验及其催化剂的表征进一步证明了这个假设,提供了在邻位导向磺化反应中确定钯价态变化的直接方法.

Co纳米颗粒低温催化合成3C-SiC纳米线及其光致发光性能

以膨胀石墨和硅粉为原料、Co(NO_(3))_(3)·6H_(2)O为催化剂前驱体,在流动Ar气中合成了3C-SiC纳米线。研究了反应温度、催化剂用量对合成3C-SiC粉体反应的影响。用第一性原理计算分析了Co纳米颗粒的催化机理,研究了3C-SiC纳米线的光致发光性能。结果表明:催化剂Co的引入降低了硅粉碳化反应生成SiC的开始反应温度和完全反应温度。催化剂Co的加入量为3%(质量分数)时,1573 K保温3 h反应后合成的3C-SiC纳米线的直径为50~60 nm,长度约几十微米,其生长机理主要为气-固反应。Co纳米颗粒与反应物之间的吸附作用降低了C=C键、C—O键和Si—O键的结合,从而促进了SiC的成核与生长。激发波长为254 nm时,3C-SiC纳米线的室温光致发光谱的特征峰在307 nm,该纳米线在光电子纳米材料领域有良好的应用前景。

纳米催化剂颗粒的热力学分析

本文综述了纳米催化剂颗粒的制备方法和其在某些领域中的应用。另外简单介绍了溶胶-凝胶法、微乳液法等制备纳米粒子的方法和纳米催化剂在化学电源、光催化降解、尾气处理等领域内的应用。重点讨论了纳米催化剂颗粒形成的热力学分析、纳米催化剂颗粒催化性能的热力学分析。

Hydrothermal synthesis of titanium-supported nanoporous palladium-copper electrocatalysts for formic acid oxidation and oxygen reduction reaction

Nanoporous Pd and binary Pd-Cu particles were prepared by a hydrothermal method using ethylene glycol as a reduction agent and they were directly immobilized on Ti substrates named as Ti-supported Pd-based catalysts. Their electrocatalytic activity for formic acid oxidation and oxygen reduction reaction （ORR） in alkaline media was examined by voltammetric techniques. Among the as-prepared catalysts, nanoPdslCu19/Ti catalyst presents the highest current density of 39.8 mA/cm2 at -0.5 V or 66.4 mA/cm2 at -0.3 V for formic acid oxidation. The onset potential of ORR on the nanoPdslCU19/Ti catalyst presents an about 70 mV positive shift compared to that on the nanoPd/Ti, and the current density of ORR at -0.3 V is 2.12 mA/cm2, which is 3.7 times larger than that on the nanoPd/Ti.

Ag-Ni alloy nanoparticles for electrocatalytic reduction of benzyl chloride

Ag-based nanocatalysts exhibit good catalytic activity for the electrochemical reduction of organic halides. Ag-Ni alloy nanoparticles（NPs） were facilely prepared by chemical reduction, and the as-prepared nanocatalysts were characterized by X-ray diffraction, ultraviolet-visible spectroscopy, transmission electron microscopy and energy-dispersive X-ray spectroscopy. The electrocatalytic activity of Ag-Ni NPs for benzyl chloride reduction was studied in organic medium using cyclic voltammetry, chronoamperometry and electrochemical impedance spectroscopy. The results show that the addition of Ni element can obviously decrease the size of Ag-Ni NPs, shift the reduction peak potential（φp） of benzyl chloride positively, and increase the catalytic activity of Ag-Ni NPs. However, when the Ni content reaches a certain value, the catalytic activity of Ag-Ni NPs decreases. Meanwhile, the synergistic catalytic effect of Ag-Ni NPs was also discussed.

Preparation and photocatalytic performance of Cu-doped TiO_2 nanoparticles

Cu-doped TiO2 nanoparticles with different doping contents from 0 to 2.0% （mole fraction） were synthesized through sol-gel method. X-ray diffraction （XRD）, X-ray photoelectron spectroscopy （XPS） and field emission scanning electron microscope （FE-SEM） were used to characterize the crystalline structure, chemical valence states and morphology of TiO2 nanoparticles. UV-Vis absorption spectrum was used to measure the optical absorption property of the samples. The photocatalytic performance of the samples was characterized by degrading 20 mg/L methyl orange under UV-Vis irradiation. The results show that the Cu-doped TiO2 nanoparticles exhibit a significant increase in photocatalytic performance over the pure TiO2 nanoparticles, and the TiO2 nanoparticles doped with 1.0% Cu show the best photocatalytic performance. The improvement in photocatalytic performance is attributed to the enhanced light adsorption in UV-Vis range and the decrease of the recombination rate of photoinduced electron-hole oair of the Cu-doped TiO2 nanoparticles.

Effect of nickel phosphide nanoparticles crystallization on hydrogen evolution reaction catalytic performance

In order to investigate the effect of nickel phosphide nanoparticles’ （Ni-P NPs） crystallization on hydrogen evolution reaction （HER） catalytic performance, amorphous Ni-P NPs and crystalline Ni12P5 were synthesized by a simple and low-cost autocatalytic reduction method and heat treatment process. The result of electrochemical tests shows that crystalline Ni12P5 has much higher HER catalytic activity than the amorphous one. X-ray diffraction, transmission electron microscopy and X-ray photoelectron spectroscopy revealed that Ni？P bond formed during crystallization, making Ni positively charged and P negatively charged. This charged nature of Ni12P5 is similar to [NiFe] hydrogenase and its analogous, which make the removal of H2 less energy-cost.

Octahedral Cu_2O-modified TiO_2 nanotube arrays for efficient photocatalytic reduction of CO_2

A photocatalyst composed of TiO 2 nanotube arrays（TNTs） and octahedral Cu2 O nanoparticles was fabricated,and its performance in the photocatalytic reduction of CO2 under visible and simulated solar irradiation was studied. The average nanotube diameter and length was 100 nm and 5 μm,respectively. The different amount of octahedral Cu2 O modified TNTs were obtained by varying electrochemical deposition time. TNTs modified with an optimized amount of Cu2 O nanoparticles exhibited high efficiency in the photocatalysis,and the predominant hydrocarbon product was methane. The methane yield increased with increasing Cu2 O content of the catalyst up to a certain deposition time,and decreased with further increase in Cu2 O deposition time. Insufficient deposition time（5 min） resulted in a small amount of Cu2 O nanoparticles on the TNTs,leading to the disadvantage of harvesting light. However,excess deposition time（45 min） gave rise to entire TNT surface being most covered with Cu2 O nanoparticles with large sizes,inconvenient for the transport of photo-generated carriers. The highest methane yield under simulated solar and visible light irradiation was observed for the catalysts prepared at a Cu2 O deposition time of 15 and 30 min respectively. The morphology,crystallization,photoresponse and electrochemical properties of the catalyst were characterized to understand the mechanism of its high photocatalytic activity. The TNT structure provided abundant active sites for the adsorption of reactants,and promoted the transport of photogenerated carriers that improved charge separation. Modifying the TNTs with octahedral Cu2 O nanoparticles promoted light absorption,and prevented the hydrocarbon product from oxidation. These factors provided the Cu2O-modified TNT photocatalyst with high efficiency in the reduction of CO2,without requiring co-catalysts or sacrificial agents.

A review of significant factors in the synthesis of hetero-structured dumbbell-like nanoparticles

This paper reviews several important factors that influence the synthesis of dumbbell‐like nanoparticles,which can significantly enhance the catalyst activity in catalytic combustion. The dumbbell‐like nanoparticles discussed in this article refer to a hetero‐structure with two nanoparticles of different materials in contact with each other. This nanostructure can be considered as a special intermediate between individual spherical nanoparticles and a core–shell nanostructure. Therefore,the synthesis of dumbbell‐like nanoparticles is more difficult than other structures. The controllability of the synthesis process, the nanoparticle size and size distribution, and the morphology of the final products depend on many factors： the seed size and size ratio could be used to influence the controllability of epitaxial growth. The component sizes and size distribution could be varied by carefully controlling the reaction temperature and reaction time. The morphology of the dumbbell‐like nanoparticles is closely related to the solvent polarity, the precursor ratio, the lattice mismatch between the two components, and the surfactant concentration. Some related synthesis methods are also briefly introduced in each section to facilitate understanding. This summary will benefit the development of new dumbbell‐like nanoparticles with various components, which have great potential in catalytic combustion of more dysoxidizable gases.

Metal–organic-framework-based catalysts for hydrogenation reactions

Metal-organic-framework （MOF）-based materials with novel physicochemical properties have emerged as promising catalysts for various hydrogenation reactions. In addition to metal clusters and multifunctional organic ligands, MOF-based catalysts can incorporate other functional species, and thus provide various active sites for hydrogenation processes. The structural properties of the catalysts play significant roles in enhancing the interactions among the reactants, products, and catalytic sites, which can be rationally designed. Because of the synergistic effects between the ac-tive sites and the structural properties, MOF-based catalysts can achieve higher activities and selec- tivities in hydrogenation reactions than can be obtained using traditional heterogeneous catalysts. This review provides an overview of recent developments in MOF-based catalysts in the hydro-genation of alkenes, alkynes, nitroarenes, cinnamaldehyde, furfural, benzene, and other compounds. Strategies for improving the catalytic performances of MOF-based catalysts are discussed as well as the different active sites and structural properties of the catalysts.

Fabrication and photocatalytic properties of Cu_2S/T-ZnO_w heterostructures via simple polyol process

The Cu2S/tetrapod-like ZnO whisker（T-ZnOw） heterostructures were successfully synthesized via a simple polyol process employing the poly（vinyl pyrrolidone）（PVP） as a surfactant.The as-prepared heterostructures were characterized by X-ray diffraction（XRD）,field emission scanning electron microscopy（FESEM）,X-ray photoelectron spectroscopy（XPS） and Fourier transform infrared（FTIR）.The photocatalytic properties of Cu2S/T-ZnOw nanocomposites synthesized with different PVP concentrations were evaluated by photodegradation of methyl orange（MO） under UV irradiation.The results show that the Cu2S/T-ZnOw nanocomposites exhibit remarkable improved photocatalytic property compared with the pure T-ZnOw.The sample prepared with 3.0 g/L PVP shows an excellent photocatalytic property and the highest photodegradation rate of MO is 97% after UV irradiation for 120 min.Besides,the photocatalytic activity of the photocatalyst has no evident decrease even after four cycles,which demonstrates that the Cu2S/T-ZnOw photocatalyst exhibits an excellent photostability.Moreover,the photocatalytic mechanism of the Cu2S/T-ZnOw nanocomposites was also discussed.

Mn nanoparticles enhanced dehydrogenation and hydrogenation kinetics of MgH_(2) for hydrogen storage

Mn nanoparticles(nano-Mn)were successfully synthesized and doped into MgH_(2) to improve its de/hydrogenation properties.Compared with MgH_(2),the onset desorption temperature of 10 wt.%nano-Mn modified MgH_(2) was decreased to 175℃ and 6.7,6.5 and 6.1 wt.%hydrogen could be released within 5,10 and 25 min at 300,275 and 250℃,respectively.Besides,the composite started to take up hydrogen at room temperature and absorbed 2.0 wt.%hydrogen within 30 min at low temperature of 50℃.The hydrogenation activation energy of MgH_(2) was reduced from(72.5±2.7)to(18.8±0.2)kJ/mol after doping with 10 wt.%nano-Mn.In addition,the MgH_(2)+10 wt.%nano-Mn composite exhibited superior cyclic property,maintaining 92%initial capacity after 20 cycles.

Preparation of Nitrogen-doped TiO2 Nanoparticle Catalyst and Its Catalytic Activity under Visible Light

N-doped TiO2 nanoparticle photocatalysts were prepared through a sol-gel procedure using NH4C1 as the nitrogen source and followed by calcination at certain temperature. Systematic studies for the preparation parameters and their impact on the structure and photocatalytic activity under ultraviolet （UV） and visible light irra-diation were carried out. Multiple techniques （XRD, TEM, DRIF, DSC, and XPS） were commanded to characterize the crystal structures and chemical binding of N-doped TiO2. Its photocatalytic activity was examined by the deg- radation of organic compounds. The catalytic activity of the prepared N-doped TiO2 nanoparticles under visible light （λ〉400nm） irradiation is evidenced by the decomposition of 4-chlorophenol, showing that nitrogen atoms in the N-doped TiO2 nanoparticle catalyst are responsible for the visible light catalytic activity. The N-doped TiO2 nanoparticle catalyst prepared with this modified route exhibits higher catalytic activity under UV irradiation in contrast to TiO2 without N-doping. It is suggested that the doped nitrogen here is located at the interstitial site of TiO2 lattice.

Preparation of amphiphilic TiO_2 Janus particles with highly enhanced photocatalytic activity

Stearic-acid-modified TiO2 (STA-TiO2) particles were prepared via the impregnation approach and used as a precursor for preparing TiO2 Janus particles. The morphology, structure, and properties of the TiO2 Janus particles were characterized using Fourier-transform infrared spectroscopy, ultraviolet- visible diffuse reflectance spectroscopy, thermogravimetric analysis, fluorescence microscopy, high-resolution transmission electron microscopy, contact angle analysis, dynamic light scattering, biological microscopy, X-ray photoelectron spectroscopy, and electrochemical impedance spectroscopy measurements. The results show that TiO2 Janus particles can be successfully prepared via toposelective surface modification. STA grafted on the surface of TiO2 enhances its hydrophobicity, promotes charge separation, and improves its adsorption capacity for organic compounds. The TiO2 Janus particles strongly adsorb on an oil-water interface to form a stable Pickering emulsion. The degradation rates of high-concentration kerosene and nitrobenzene wastewaters when the photocatalyst is pure TiO2, STA-TiO2, or TiO2 Janus particles are discussed and compared. The degradation rates were determined using an ultraviolet-visible spectrophotometer. It was found that the Pickering emulsion stabilized by the TiO2 Janus particles exhibited the best photocatalytic performance;these Janus particles show promising potential for catalytic application.

Bifunctional S-scheme g-C3N4/Bi/BiVO4 hybrid photocatalysts toward artificial carbon cycling

Although both the aerobic photocatalytic oxidation of organic pollutants into CO2 and the anaerobic photocatalytic reduction of CO2 into solar fuels have been intensively studied,few efforts have been devoted to combining these carbon-involved photocatalytic oxidation-reduction processes together,by which an artificial photocatalytic carbon cycling process can be established.The key challenge lies in the exploitation of efficient bifunctional photocatalysts,capable of triggering both aerobic oxidation and anaerobic reduction reactions.In this work,a bifunctional ternary g-C3N4/Bi/BiVO4 hybrid photocatalyst is successfully constructed,which not only demonstrates superior aerobic photocatalytic oxidation performance in degrading an organic pollutant(using the dye,Rhodamine B as a model),but also exhibits impressive photocatalytic CO2 reduction performance under anaerobic conditions.Moreover,a direct conversion of Rhodamine B to solar fuels in a one-pot anaerobic reactor can be achieved with the as-prepared ternary g-C3N4/Bi/BiVO4 hybrid photocatalyst.The excellent bifunctional photocatalytic performance of the g-C3N4/Bi/BiVO4 photocatalyst is associated with the formation of efficient S-scheme hybrid junctions,which contribute to promoting the appropriate charge dynamics,and sustaining favorable charge potentials.The formation of the S-scheme heterojunction is supported by scavenger studies and density functional theory calculations.Moreover,the in-situ formed plasmonic metallic Bi nanoparticles in the S-scheme hybrid g-C3N4/Bi/BiVO4 photocatalyst enhances vectorial interfacial electron transfer.This novel bifunctional S-scheme g-C3N4/Bi/BiVO4 hybrid photocatalyst system provides new insights for the further development of an integrated aerobic-anaerobic reaction system for photocatalytic carbon cycling.