Significantly enhanced hydrogen desorption properties of Mg(AlH4)2 nanoparticles synthesized using solvent free strategy

Mg(AlH_4)_2 nanoparticles with a particle size less than 10 nm have been successfully synthesized by mechanochemical method using LiAlH_4 and MgCl_2 as raw materials together with Li Cl buffering additive. In comparison to Mg(AlH_4)_2 microparticles, Mg(AlH_4)_2 nanoparticles exhibit a faster hydrogen desorption kinetics and lower desorption temperature. The hydrogen desorption temperatures of the first and second dehydrogenation steps are 80 and 220 °C for the Mg(AlH_4)_2 nanoparticles, which are about 65 and 60 °C, respectively, lower than those of Mg(AlH_4)_2 microparticles. The decomposition activation energy is reduced from 135 k J/mol for Mg(AlH_4)_2 microparticles to 105.3 k J/mol for Mg(AlH_4)_2 nanoparticles. It is proposed that the shortened diffusion distance and enhanced diffusivity of Mg(AlH_4)_2/MgH_2 nanoparticles provide an energy destabilization for lowering the dehydrogenation temperature, and thus being the key factor for promoting the hydrogen desorption kinetics. More importantly, it is demonstrated that the dehydrided nano MgH_2 hydride with a particle size below 10 nm can be formed after rehydrogenation process, resulting in the good cycling hydrogen desorption performance of nano MgH_2.     

Cs-Mg-H合金的形成能力与成键机制研究

采用基于密度泛函理论第一性原理的Vienna Ab initio Simulation Package (VASP)软件研究了CsMgH₃, Cs₄Mg₃H₁₀和Cs₂MgH₄氢化物的晶体结构、反应焓和电子结构. 结果表明 CsMgH₃, Cs₄Mg₃H₁₀和Cs₂MgH₄都能直接由单质Cs和Mg在H₂中反应生成, 其中Cs₄Mg₃H₁₀的形成能力最强; 态密度和电荷密度的分析与讨论表明了Mg和H的成键机制为离子键伴随着显著的共价键.     

Hydrogen storage properties of MgH2 co-catalyzed by LaH3 and NbH

To improve the hydrogen storage properties of Mg-based alloys, a composite material of MgH2 + 10wt%LaH3 + 10wt%NbH was prepared by a mechanical milling method. The composite exhibited favorable hydrogen desorption properties, releasing 0.67wt% H2 within 20 min at 548 K, which was ascribed to the co-catalytic effect of LaH3 and NbH upon dehydriding of MgH2. By contrast, pure MgH2, an MgH2 + 20wt%LaH3 composite, and an MgH2 + 20wt%NbH composite only released 0.1wt%, 0.28wt%, and 0.57wt% H2, respectively, un-der the same conditions. Analyses by X-ray diffraction and scanning electron microscopy showed that the composite particle size was small. Energy-dispersive X-ray spectroscopic mapping demonstrated that La and Nb were distributed homogeneously in the matrix. Differential thermal analysis revealed that the dehydriding peak temperature of the MgH2 + 10wt%LaH3 + 10wt%NbH composite was 595.03 K, which was 94.26 K lower than that of pure MgH2. The introduction of LaH3 and NbH was beneficial to the hydrogen storage performance of MgH2.     

An effective amperometric biosensor based on graphene modified gold nanowire arrays for glucose detection

A novel glucose biosensor based on graphene nanosheets （GNs） modified gold nanowire arrays （AuN- WAs） electrode was constructed. Highly ordered gold nanowire arrays were prepared by direct electrodeposition in anodic aluminum oxide templates. GNs were synthe- sized through a public route involving graphite oxidation, exfoliation, and chemical reduction. Field emission scan- ning electron microscope and high-resolution transmission electron microscope were employed to characterize the as- prepared AuNWAs and GNs. Glucose oxidase was immobilized on the surface of GNs-AuNWAs modified electrode via a cross-linking method. The cyclic voltam- metry results showed that the GNs-AuNWAs-based glu- cose biosensors have high catalysis activity to hydrogen peroxide （H2O2） than those modified with GNs or AuN- WAs only. Furthermore, amperometric response was employed to detect glucose concentration owing to its simplicity, high selectivity, and relative low cost. Glucose biosensors based on GNs-AuNWAs showed excellent performance with high sen- sitivity of 40.25 μA cm^-2 （mmol/L）^-1, low detection limit of 0.02 mmol/L, and a linear range from 0.02 to 3 mmol/L.     

Synergic catalytic effect of Ti hydride and Nb nanoparticles for improving hydrogenation and dehydrogenation kinetics of Mg-based nanocomposite

The Mg-9.3 wt% (TiH1.971-TiH)?0.7 wt% Nb nanocomposite has been synthesized by hydrogen plasma-metal reaction (HPMR) approach to enhance the hydrogen sorption kinetics of Mg at moderate temperatures by providing nanosizing effect of increasing H “diffusion channels” and adding transition metallic catalysts. The Mg nanoparticles (NPs) were in hexagonal shape range from 50 to 350 nm and the average size of the NPs was 177 nm. The small spherical TiH1.971, TiH and Nb NPs of about 25 nm uniformly decorated on the surface of the big Mg NPs. The Mg-TiH1.971-TiH-Nb nanocomposite could quickly absorb 5.6 wt% H2 within 5 min at 573 K and 4.5 wt% H2 within 5 min at 523 K, whereas the pure Mg prepared by HPMR could only absorb 4 and 1.5 wt% H2 at the same temperatures. TiH1.971, TiH and Nb NPs transformed into TiH2 and NbH during hydrogenation and recovered after dehydrogenation process. The apparent activation energies of the nanocomposite for hydrogenation and dehydrogenation were 45.0 and 50.7 kJ mol?1, which are much smaller than those of pure Mg NPs, 123.8 and 127.7 kJ mol?1. The improved sorption kinetics of the Mg-based nanocomposite at moderate temperatures and the small activation energy can be interpreted by the nanostructure of Mg and the synergic catalytic effects of Ti hydrides and Nb NPs.     

Recent advances in additive-enhanced magnesium hydride for hydrogen storage

The discovery of new hydrogen storage materials has greatly driven the entire hydrogen storage technology forward in the past decades. Magnesium hydride, which has a high hydrogen capacity and low cost, has been considered as one of the most promising candidates for hydrogen storage. Unfortunately, extensive efforts are still needed to better improve its hydrogen storage performance, since MgH2 suffers from high operation temperature, poor dehydrogenation kinetic, and unsatisfactory thermal management. In this paper, we present an overview of recent progress in improving the hydrogenation/de-hydrogenation performance of MgH2, with special emphases on the additive-enhanced MgH2 composites. Other widely used strategies (e. g. alloying, nanoscaling, nanoconfinement) in tuning the kinetics and thermodynamics of MgH2 are also presented. A realistic perspective regarding to the challenges and opportunities for further researches in MgH2 is proposed.     

石墨烯与掺N石墨烯对甲酸盐电氧化催化剂Pt和Pd抗毒性的提升研究

为研究载体对甲酸盐电氧化催化剂抗毒性的促进作用,将商用催化剂Pt/C和Pd/C分别与石墨烯(GNs)及掺N石墨烯(NGNs)超声混合后涂制电极,通过循环伏安法(CV)及计时电流法(CA)比较了混合GNs及NGNs对催化剂抗毒性的影响.结果表明,加入GNs和NGNs均可提高Pt/C与Pd/C的抗毒性,其中NGNs提升作用更显著.该研究表明,石墨烯类材料改善催化剂抗毒性具有普适意义.     

石墨烯对铜纳米复合材料物理力学性能和摩擦学性能的影响

本文对铜–石墨烯纳米片（GN）纳米复合材料的力学性能和摩擦学性能进行了实验研究。我们采用化学包覆法将银粒子包覆在GNs上,以避免其与铜的反应和金属间相的形成。分析了GN含量对制备的纳米复合材料的结构、力学性能和摩擦学性能的影响。结果表明,化学镀是一种有效避免铜与碳反应和金属间相形成的方法。GNs的加入显著提高了Cu纳米复合材料的力学性能和摩擦学性能。然而,GNs的添加需要谨慎进行,因为在达到一定的阈值后,其机械性能和摩擦学性能会受到负面影响。结果表明,GN含量为0.5vol%时,复合材料的硬度、磨损率和摩擦系数分别比铜纳米复合材料提高了13%、81.9%和49.8%。这些改进的性能是由于降低的晶体尺寸,GNs的存在,以及复合材料成分的均匀分布。     

Electrochemical hydrogen storage properties of Mg100−xNix produced by hydriding combustion synthesis and mechanical milling

In this work, Mg-based hydrogen storage composites with an initial 100-x: x (x=25, 32.3, 50, 66.7) of Mg:Ni molar ratio were prepared by HCS+MM and their phase compositions and electrochemical performances were investigated in detail. The results show that the composites with desirable constituents can be achieved by adjusting the molar ratio of the starting materials in the HCS process. Particularly, the HCS product of Mg67.7Ni32.3 consists of the principal phase Mg2NiH4 and minor phase Mg2NiH0.3. The dominate phase varies from Mg2NiH0.3 and MgH2 for the Mg enriched sample (x<32.3) to MgNi2 and Ni for the Ni enriched sample (x>32.3). The MM modification not only brings about grain refinement of the alloys, but also leads to phase transformation of part Mg2NiH4 to Mg2NiH0.3 in the Mg67.7Ni32.3 sample. Electrochemical tests indicate that each sample can reach its maximum discharge capacity at the first cycle. Mg67.7Ni32.3 displays the highest discharge capacity as well as a superior electrochemical kinetics owing to its excellent H atom diffusion ability and lower charge-transfer resistance. The Mg67.7Ni32.3 provides the most optimized Mg/Ni atomic ratio considering the comprehensive electrochemical properties of all samples.     

焙烧温度对Cu/Mg/Al催化剂催化纤维素转移加氢液化的影响

固定Cu/Mg/Al物质的量比15∶60∶25,采用共沉淀法制备Cu/Mg/Al水滑石前驱体,经过不同温度焙烧制得一系列用于纤维素在高温高压甲醇中转移加氢液化的催化剂.采用XRD、TG/DTG、BET、H2-TPR和FT-IR等表征手段研究了焙烧温度对Cu/Mg/Al水滑石衍生催化剂性能的影响.结果表明水滑石经过450 ℃焙烧后,热分解较为完全,CuO与载体MgO之间相互作用良好,具有优异的稳定结构,且CuO易还原,催化性能好.当焙烧温度450 ℃,催化剂结晶效果差,稳定性差,导致催化剂活性低.而焙烧温度450 ℃时,催化剂中CuO因为高温发生团聚,并且高温(≥650 ℃)焙烧后起隔离分散作用的尖晶石MgAl2O4稳定性较差,在参与纤维素液化的高温高压反应过程中会发生分解,导致CuO发生二次团聚;此外催化剂还会发生烧结现象使催化剂活性降低.     

Co/CFs的制备及其电催化析氢性能研究

 以木质纤维素为基体,采用浸渍、高温碳化的方法制备了木质碳纤维负载的钴纳米颗粒（Co/CFs）电催化剂。利用X射线衍射（XRD）、X射线光电子能谱（XPS）、扫描电子显微镜（SEM）、透射电子显微镜（TEM）等对样品的化学组成和微观形貌进行了表征分析,并借助电化学工作站测试了样品的电催化析氢性能。结果表明,CFs的引入有效缓解了Co纳米颗粒（Co NPs）易团聚的问题,有利于实现活性位点的最大程度暴露。当Co/CFs用作析氢催化剂,达到10 mA·cm^-2的电流密度时需要的过电位仅为250 mV,并可保持长达15 h的催化稳定性。     

Effects of the flow rate of hydrogen on the growth of graphene

Graphene samples with different morphologies were fabricated on the inside of copper enclosures by low pressure chemical vapor deposition and tuning the flow rate of hydrogen. It is found that the flow rate of hydrogen greatly influences the growth of graphene. Thermodynamic analysis indicates that a higher flow rate of hydrogen is favorable to the formation of good quality graphene with regular morphology. However, the mass-transfer process of methane dominates the growth driving force. At very low pressure, mass-transfer proceeds by Knudsen diffusion, and the mass-transfer flux of methane decreases as the flow rate of hydrogen increases, leading to a decrease in the growth driving force. At a higher pressure, mass-transfer proceeds by Fick's diffusion, and the mass-transfer flux of methane is dominated by the gas velocity, whose variation determines the growth driving force variation of graphene.     

Graphene-reinforced aluminum matrix composites prepared by spark plasma sintering

Graphene-reinforced 7055 aluminum alloy composites with different contents of graphene were prepared by spark plasma sintering (SPS). The structure and mechanical properties of the composites were investigated. Testing results show that the hardness, compressive strength, and yield strength of the composites are improved with the addition of 1wt% graphene. A clean, strong interface is formed between the metal matrix and graphene via metallurgical bonding on atomic scale. Harmful aluminum carbide (Al₄C₃) is not formed during SPS processing. Further addition of graphene (above 1wt%) results in the deterioration in mechanical properties of the composites. The agglomeration of graphene plates is exacerbated with increasing graphene content, which is the main reason for this deterioration.     

石墨烯/离子液体/壳聚糖/血红蛋白修饰玻碳电极检测过氧化氢

将石墨烯、离子液体(1-丁基-3-甲基-咪唑四氟硼酸盐)与壳聚糖结合,制备了一种新型的石墨烯-离子液体/壳聚糖纳米复合膜修饰玻碳电极.用循环伏安法研究了血红蛋白在该修饰电极上的直接电化学行为.结果表明,血红蛋白在该纳米复合膜电极上对过氧化氢具有良好的催化性能.过氧化氢的电流响应信号与其浓度在0.1～500μmol/L范围内呈线性关系,检出限为0.02μmol/L(RSN=3),为过氧化氢检测提供了一种灵敏的新方法.     

偏硼酸钠与镁和氢反应的硼氢化钠生成(英文)

高的氢压和反应温度有利于片硼酸钠与镁和氢反应生成硼氢化钠,但温度接近镁的熔点时不利于硼氢化钠的生成。在反应物中添加铁、镍和钴将加速硼氢化钠的生成,而铜的加入却阻碍硼氢化钠的生成。     

石墨烯纳米薄片的制备及其作为DSCs对电极的光电性能

采用氧化还原法制备出多层结构的石墨烯纳米薄片（GNs）,分析了还原阶段水浴时间对GNs晶体结构的影响,着重探讨了GNs作为染料敏化太阳电池（DSCs）对电极催化层的光电性能及阻抗特征。结果表明,还原阶段水浴反应时间为24h时制备出的GNs平均层数最薄,平均厚度只有7层,将该反应时间制备出的GNs对电极组装成DSCs后,其短路电流（JSC）及填充因子（FF）明显地比石墨和氧化石墨（GO）对电极组装成DSCs的JSC和FF要高,因此使得其转换效率达到最好,为1.17%,比石墨和氧化石墨（GO）对电极分别增加了0.175%和1.034%。阻抗分析发现,GNs对电极的串阻（Rs）明显的减小,从而使得GNs作为染料敏化太阳电池（DSCs）对电极催化层的光电性能达到最佳。     

石墨烯场效应晶体管电子识别葡萄糖

以铜箔为衬底,采用化学气相沉积的方法制备大面积单层石墨烯薄膜并制备相应的石墨烯场效应晶体管,过氧化氢电子识别研究表明,石墨烯场效应晶体管的电性能对由过氧化氢产生的外来干扰非常灵敏。利用末端带有吡啶环功能基团的葡萄糖氧化酶对石墨烯场效应晶体管进行表面改性后,葡萄糖电子识别结果表明其器件对葡萄糖有非常灵敏的电子识别性能,其检测下限小于0.1 mM,且具有生物传感器响应快、稳定性好的特点。     

快淬Mg2Ni型合金的结构及贮氢动力学

用快淬技术制备Mg2-xLaxNi(x=0,0.2,0.4,0.6)贮氢合金,用XRD,SEM和HRTEM分析合金的微观组织结构;测试合金的气态及电化学贮氢动力学。结果表明:快淬二元Mg2Ni合金具有典型的纳米晶结构,而快淬La替代合金明显地具有非晶结构,La替代Mg提高Mg2Ni型合金的非晶形成能力。La替代Mg明显地改变Mg2Ni型合金的相组成,当x=0.4时,合金的主相改变为(La,Mg)Ni3+LaMg3。快淬及La替代明显影响合金的气态及电化学贮氢动力学,La替代使合金的吸氢动力学先降低后增加,但使合金的气态脱氢及电化学贮氢动力学先增加后降低。快淬对合金气态及电化学贮氢动力学的影响与合金的成分相关,对于La0.4合金,合金的气态吸氢动力学随淬速的增加先增加后减小,其放氢动力学随淬速的增加而增加。     

不同工艺条件对半固态挤压Mg2 Si/Al复合材料组织和性能的影响

采用等温热处理半固态挤压的方法制备Mg2Si/Al复合材料,研究等温热处理温度、保温时间和挤压比压对复合材料组织和布氏硬度的影响.结果表明:经过等温热处理后得到了基体α-Al和Mg2Si增强相双球化的半固态组织,其中,Mg2Si颗粒呈现球化,α-Al呈现规则球形或椭球形.当挤压比压恒定时,Mg2Si/Al复合材料显微组织中α-Al和Mg2Si颗粒的球化随着温度和保温时间的增加而更加明显,同时α-Al的粗化也更加明显;当等温热处理温度和保温时间恒定时,挤压比压对半固态挤压Mg2Si/Al复合材料显微组织的影响不大.硬度测试表明,当挤压比压恒定时,布氏硬度随着等温热处理温度和保温时间的增加呈现先增加后减小的趋势;但当等温热处理温度和保温时间恒定时,随着挤压比压的增加,布氏硬度随之提高.     

nc-Si:H薄膜的微结构特征与光学特性

利用射频等离子体增强型化学气相沉积(RF-PECVD)工艺,以SiH4和H2作为反应气体源,在玻璃和石英衬底上制备了氢化纳米晶硅(nc-Si:H)薄膜.采用Raman散射谱、原子力显微镜(AFM)、透射光谱方法对在不同衬底温度与不同H2稀释比条件下沉积生长薄膜的微结构和光学特性进行了实验研究.结果表明,nc-Si:H薄膜的晶粒尺寸为2.6～7.0nm和晶化率为45%～48%.在一定反应压强、衬底温度和射频功率下,随着H2稀释比的增加,薄膜的沉积速率降低,但晶化率和晶粒尺寸均有所增加,相应光学吸收系数增大.而在一定反应压强、射频功率和H2稀释比下,随着衬底温度的增加,沉积速率增加,薄膜晶化率提高.