One-step synthesis of magnetically recyclable Au/Co/Fe triple-layered core-shell nanoparticles as highly efficient catalysts for the hydrolytic dehydrogenation of ammonia borane

Magnetically recyclable Au/Co/Fe core-shell nanoparticles (NPs) have been successfully synthesized via a one-step in situ procedure. Transmission electron microscope (TEM), energy dispersive X-ray spectroscopic (EDS), and electron energy-loss spectroscopic (EELS) measurements revealed that the trimetallic Au/Co/Fe NPs have a triple-layered core-shell structure composed of a Au core, a Co-rich inter-layer, and a Fe-rich shell. The Au/Co/Fe core-shell NPs exhibit much higher catalytic activities for hydrolytic dehydrogenation of ammonia borane (NH₃BH₃, AB) than the monometallic (Au, Co, Fe) or bimetallic (AuCo, AuFe, CoFe) counterparts.      

Hydrolytic dehydrogenation of ammonia borane catalyzed by poly(amidoamine) dendrimers-modified reduced graphene oxide nanosheets supported Ag0.3Co0.7 nanoparticles

Poly(amidoamine) dendrimers-modified reduced graphene oxide nanosheets (PAMAM/rGO) composite was selected as a carrier of heterogeneous Ag_0.3Co_0.7 nanoparticles in order to obtain an excellent catalyst for ammonia borane (AB) hydrolysis. During the synthetic processes, GO could easily assembled with PAMAM by the electrostatic and hydrogen-bonding interactions. Structural characterization revealed that Ag_0.3Co_0.7 bimetallic nanoparticles with uniform size distribution of 5 nm are well dispersed on PAMAM/rGO composite architecture. Ag_0.3Co_0.7@PAMAM/rGO was found to be a highly active and reusable catalyst in hydrogen generation from the hydrolysis of AB with a turnover frequency value (TOF) of 19.79 mol_H2 min^–1 mol_M^–1 at 25.0 ± 0.1 °C and retained 75.4% of their initial activity with a complete release of hydrogen in five runs. The relatively high TOF value and low apparent activation energy (34.21 kJ mol^–1) make these Ag_0.3Co_0.7@PAMAM/rGO NPs as a high-efficient catalyst for catalytic dehydrogenation of AB facilitating the development of practically applicable energy storage materials.     

Ni nanoparticles supported on carbon as efficient catalysts for the hydrolysis of ammonia borane

We report on the preparation of three kinds of Ni nanoparticles supported on carbon （Ni/C） and their application in the catalytic hydrolysis of ammonia borane （AB）. Three Ni/C catalysts were prepared from a Ni metal-organic framework （Ni-MOF） precursor by reduction with KBI-G calcination at 700 ℃ under Ar, and a combination of calcination and reduction, the products being denoted as Ni/C-1, Ni/C-2, and Ni/C-3, respectively. The structure, morphology, specific surface area, and element valence were characterized by X-ray diffraction （XRD）, scanning electron microscopy （SEM）, transmission electron microscopy （TEM）, nitrogen adsorption-desorption measurements, and X-ray photoelectron spectra （XPS）. The results demonstrate that Ni/C-1 is composed of amorphous Ni particles agglomerated on carbon, Ni/C-2 is characteristic of crystalline Ni nanoparticles （about 10 nm in size） supported on carbon with Ni oxidized on the surface, while the surface of the Ni particles in Ni/C-3 is less oxidized. The specific surface areas of Ni-MOF, Ni/C-1, Ni/C-2, and Ni/C-3 are 1239, 33, 470, and 451 m2·g-1, respectively. The catalytic hydrolysis of AB with Ni/C-3 shows a hydrogen generation rate of 834 mL-min^-1·g-1 at room temperature and an activation energy of 31.6 kJ/mol. Ni/C-3 shows higher catalytic activity than other materials, which can be attributed to its larger surface area of crystalline Ni. This study offers a promising way to replace noble metal by under ambient conditions. Ni nanoparticles for AB hydrolysis     

Enhanced catalytic activity of monodispersed AgPd alloy nanoparticles assembled on mesoporous graphitic carbon nitride for the hydrolytic dehydrogenation of ammonia borane under sunlight

We address the composition-controlled synthesis of monodispersed AgPd alloy nanoparticles (NPs),their assembly for the first time on mesoporous graphitic carbon nitride (mpg-C3N4),and the unprecedented catalysis of mpg-C3N4@AgPd in the hydrolytic dehydrogenation of ammonia borane (AB) at room temperature.Monodispersed AgPd alloy NPs were synthesized using a high-temperature organic-phase surfactant-assisted protocol comprising the co-reduction of silver(Ⅰ) acetate and palladium(Ⅱ) acetylacetonate in the presence of oleylamine,oleic acid,and 1-octadecene.This protocol allowed the synthesis of four different compositions of AgPd alloy NPs.The AgPd alloy NPs were then assembled on mpg-C3N4,reduced graphene oxide,and Ketjenblack using a liquid-phase self-assembly method.Among the three supports tested,the mpg-C3N4@AgPd catalysts provided the best activity because of the Mott-Schottky effect,which was driven by the favorable work function difference between mpg-C3N4 and the metal NPs.Moreover,the activity of the mpg-C3N4@AgPd catalyst was further enhanced by an acetic acid treatment (AAt),and a record initial turnover frequency of 94.1 mol(hydrogen)·mol(catalyst)-1·min-1 was obtained.Furthermore,the mpg-C3N4@Ag42Pd58-AAt catalyst also showed moderate durability for the hydrolysis of AB.This study also includes a wealth of kinetic data for the mpg-C3N4@AgPd-catalyzed hydrolysis of AB.     

Tailor made exfoliated reduced graphene oxide nanosheets based on oxidative-exfoliation approach

This study presents a versatile and scalable strategy of ‘oxidation controlled exfoliation’ of rGO nanosheets synthesized from both Hummers and modified Hummers method. A co-relation between degree of oxidation of graphite oxide (GO) sheets and exfoliation of resulting synthesized rGO nanosheets has been successfully developed which in turn reflects in various properties of rGO sheets. The extent of exfoliation of rGO sheets has been well analyzed by XRD, SEM, BET and TEM techniques. Moreover, the quantitative analysis of degree of oxidation of GO has been estimated from FTIR spectra using quotient law method. The variations in number of rGO layers, defect density and sp² domain size have been investigated in detail by Raman spectroscopic technique. Both qualitative-quantitative analysis of rGO nanosheets have been discussed from their SAED pattern and HR-TEM images. The optical characterization of GO and corresponding rGO nanosheets has been studied in detail by UV- Vis spectroscopic technique.     

Coupling of short DNAs with reduced graphene oxide for electronic and sensing applications

Abstract

In this article, we described an approach for coupling of short DNAs with reduced graphene oxide and thus formation of transducer layer for biological sensors. We investigated the dependence of coupling ratio on the graphene oxide reduction level. We found optimal reduction parameters and showed successful conjugation of aptamers with reduced graphene oxide. We have revealed a trend to increase aptamer conjugation efficiency with a decrease of graphene oxide reduction rate. Finally, we made biosensor structures with Π-shaped reduction pattern and showed excellent sensitivity of the sensor during thrombin exposure. These results are important for the development of flexible low-cost biosensors of a new generation.     

还原氧化石墨烯横向尺寸分布影响因素初探

化学还原剥离氧化石墨法制备的还原氧化石墨烯具有诸多优异性能,但所得还原氧化石墨烯横向尺度差异较大.利用化学还原法制备了还原氧化石墨烯,基于还原氧化石墨烯的AFM观测结果,初步统计分析了静置、磁力搅拌、离心和超声处理及它们的次序对还原氧化石墨烯横向尺寸分布的影响,结果表明后述3个步骤及次序是影响斑点状(横向尺寸＜100nm×100nm)和树叶状(横向尺寸＞500nm×500nm)还原氧化石墨烯横向尺寸分布的主要因素.     

Nanocomposite for methanol oxidation: synthesis and characterization of cubic Pt nanoparticles on graphene sheets

Abstract

We present our recent results on Pt nanoparticles on graphene sheets (Pt-NPs/G), a nanocomposite prepared with microwave assistance in ionic liquid 2-hydroxyethanaminiumformate. Preparation of Pt-NPs/G was achieved without the addition of extra reductant such as hydrazine or ethylene glycol. The Pt nanoparticles on graphene have a cubic-like shape (about 60 wt% Pt loading, Pt-NPs/G) and the particle size is 6 ± 3 nm from transmission electron microscopy results. Electrochemical cyclic voltammetry studies in 0.5 M aqueous H₂SO₄ were performed using Pt-NPs/G and separately, for comparison, using a commercially available electrocatalyst (60 wt% Pt loading, Pt/C). The electrochemical surface ratio of Pt-NPs/G to Pt/C is 0.745. The results of a methanol oxidation reaction (MOR) in 0.5 M aqueous H₂SO₄ + 1.0 M methanol for the two samples are presented. The MOR results show that the ratios of the current density of oxidation (I_f) to the current density of reduction (I_b) are 3.49 (Pt-NPs/G) and 1.37 (Pt/C), respectively, with a preference by 2.55 times favoring Pt-NPs/G. That is, the tolerance CO poisoning of Pt-NPs/G is better than that of commercial Pt/C.     

钠离子电池TiO_2/还原氧化石墨烯负极材料的制备及储钠性能

由于钠离子半径比锂离子半径大70%,使得钠离子在石墨电极材料中脱嵌较困难,需要对石墨负极材料进行改性。以天然石墨为原料,采用Hummers法制备氧化石墨烯;在此基础上以钛酸丁酯为原料,采用溶胶-凝胶法制备了TiO_2前驱体/氧化石墨烯(TiO_2/GO)复合材料,通过热处理获得锐钛矿型TiO_2/还原氧化石墨烯(TiO_2/RGO)复合材料。电化学测试结果表明:TiO_2含量为15wt%的TiO_2/RGO复合材料在电流密度为20mA·g~(-1)下的首次放电比容量为74.08mAh·g~(-1),随着循环次数的增加,放电比容量逐渐增大,循环50次后达109.10mAh·g~(-1);充放电效率也呈现出逐渐增大的趋势,循环50次后达65.59%。而纯还原氧化石墨烯首次放电比容量为41.43mAh·g~(-1),循环50次后仅为20.47mAh·g~(-1)。     

还原剂对Ni(OH)_2/还原氧化石墨烯复合材料结构及电化学性能的影响

为研究还原剂对Ni(OH)_2/还原氧化石墨烯(RGO)复合材料结构及电化学性能的影响,首先以氧化石墨烯(GO)和硝酸镍作前驱体,采用水热法制备了Ni(OH)_2/RGO复合材料;然后,利用XRD、SEM和Raman光谱仪表征了复合材料的结构和形貌,并采用循环伏安法、恒流充放电曲线和电化学阻抗谱研究了复合材料的电化学性能。结果表明:以(NH2)2CSO2作还原剂时,制备的β-Ni(OH)_2/RGO复合材料为RGO纳米片与Ni(OH)_2纳米片相互插层的结构;在电解液(6mol/L KOH溶液)中,0.2C放电倍率时β-Ni(OH)_2/RGO复合材料的比容量高达341.0mAh/g,10.0C放电倍率为时复合材料的比容量为242.2mAh/g,仍能保持β-Ni(OH)_2理论比容量的83.8%。所得结论表明制备的Ni(OH)_2/RGO复合材料显现出良好的电化学性能。     

混合氨-碱沉淀剂制备Ni(OH)_2/还原氧化石墨烯复合材料及其电化学性能

利用简单易行的化学沉淀-回流法制备了Ni(OH)_2/还原氧化石墨烯(RGO)复合材料,研究了不同混合氨-碱沉淀剂对复合材料电化学性能的影响。采用XRD、拉曼光谱(Raman)和SEM表征Ni(OH)_2/RGO复合材料的微观结构和形貌。当以NH_3·H_2O-NaOH作为沉淀剂时,Ni(OH)_2/RGO复合材料中β-Ni(OH)_2纳米片均匀分散在石墨烯片层之间,形成相互插层结构。利用循环伏安(CV)、恒电流充放电(GCD)和电化学交流阻抗(EIS)测试了复合电极材料的电化学性能。研究结果表明:放电倍率为0.2C时,Ni(OH)_2/RGO复合电极材料的放电比容量达到344.8mAh/g,比β-Ni(OH)2的放电比容量高出约29%;5C时放电比容量为274.5mAh/g,经过50个循环,容量保持率为98.8%,呈现出良好的倍率性能和循环性能。     

Self-assembly and embedding of nanoparticles by in situ reduced graphene for preparation of a 3D graphene/nanoparticle aerogel

A 3D graphene architecture can be prepared via an in situ self-assembly of graphene prepared by a mild chemical reduction. Fe(3) O(4) nanoparticles are homogeneously dispersed into graphene oxide (GO) aqueous suspension and a 3D magnetic graphene/Fe(3) O(4) aerogel is prepared during the reduction of GO to graphene. This provides a general method to prepare 3D graphene/nanoparticle composites for a wide range of applications including catalysis and energy conversion.     

Co (II) phthalocyanine - amine functionalized graphene oxide as a solid base catalyst for the oxidation of thiols

A noncovalent attachment of propylamine (PA), butylamine (BA), ethylenediamine (EDA) and tetramethylenediamine (TMD) - functionalized Graphene oxide (GO) to cobalt (II) phthalocyanine (CoPc) as a novel solid base catalyst was synthesized by mixing method. The synthesized catalysts were characterized using UV-vis, XRD, FTIR, FESEM, EDAX, MAP and HRTEM analyses. The catalytic performances of the synthesized catalyst were evaluated for the oxidation of various thiols in n-heptane under alkali free condition, and were in the following order: EDAGO-CoPc > TMDGO-CoPc > PAGO-CoPc > BAGO-CoPc. For better investigation, the potential of EDAGO-CoPc catalyst was investigated for thiols oxidation in real gasoline. According to the results, 96.55% thiols were removed from real gasoline over the EDAGO-CoPc catalyst. After eight runs of experiment, no significant change was observed in the activity of EDAGO-CoPc catalyst for thiols oxidation in real gasoline.     

Enhanced performance of TiO2/reduced graphene oxide doped by rare-earth ions for degrading phenol in seawater excited by weak visible light

La³⁺- or Yb³⁺-doped TiO₂ supported on the surface of reduced graphene oxide were fabricated by adsorbed-layer nanoreactor synthesis (ANS) coupling with a solvothermal treatment to extend photocatalysis application in the advanced treatment of simulated wastewater with high salt concentration. Results showed that La³⁺ or Yb³⁺ could distribute in the TiO₂ lattice, only in ANS preparation with graphene oxide as the carrier, to replace Ti⁴⁺ during the solvothermal treatment, thus introducing TiO₂ mixed-crystal and heterojunction structures in the catalysts. La³⁺ or Yb³⁺ caused lattice distortion structures and anionic vacancies in the TiO₂ lattice. The anionic vacancies (oxygen vacancies) might generate Ti³⁺ in catalysts, thus enhancing visible-light response, due to impurity levels introduced by La³⁺ or Yb³⁺. As the strong adsorption capability of the catalyst for phenol was not interfered by salt ions in the simulated wastewater, the catalysts could efficiently degrade phenol. The highest removal rate of phenol was approximately 90%.     

Ultrathin Co3O4 nanosheets highly dispersed on reduced graphene oxide: An efficient bi-functional catalyst for Li-O2 battery

Ultrathin Co₃O₄ nanosheets grown on the reduced graphene oxide (Co₃O₄/rGO) was synthesized by a simple hydrothermal method and was investigated as a cathode in a Li-O₂ battery. Benefited from the synergistic effect between Co₃O₄ and rGO, the hybrid exhibits a high initial capacity of 10,528 mAh g^?1 along with a high coulombic efficiency (84.4%) at 100 mA g^?1. In addition, the batteries show an enhanced cycling stability and after 113 cycles, the cut-off discharge voltage remains above 2.5 V. The outstanding performance is intimately related to the high surface area of rGO, which not only provide carbon skeleton for the uniform distribution of Co₃O₄ nanosheets but also facilitate the reversible formation and decomposition of insoluble Li₂O₂. The results of electrochemical tests confirm that the Co₃O₄/rGO hybrid is a promising candidate for the Li-O₂ batteries.