Carbon Doping Triggered Efficient Electrochemical Hydrogen Evolution of Cross-Linked Porous Ru-MoO_(2) Via Solid-Phase Reaction Strategy

The defect-free structure of Mo-based materials is a“double-edged sword”,which endows the material with excellent stability,but limits its chemical versatility and application in electrochemical hydrogen evolution reaction(HER).Carbon doping engineering is an attractive strategy to effectively improve the performance of Mo-based catalyst and maintain their stability.Herein,we report a cross-linked porous carbon-doped MoO_(2)(C–MoO_(2))-based catalyst Ru/C–MoO_(2) for electrochemical HER,which is prepared by the convenient redox solid-phase reaction(SPR)of porous RuO_(2)/Mo_(2)C composite precursor.Theoretical studies reveal that due to the presence of carbon atoms,the electronic structure of C–MoO_(2) has been properly adjusted,and the loaded small Ru nanoparticles provide a fast water dissociation rate and moderate H adsorption strength.In electrochemical studies under a pH-universal environment,Ru/C–MoO_(2) electrocatalyst exhibits a low overpotential at a current density of 10 mA cm^(-2) and has a low Tafel slope.Meanwhile,Ru/C-MoO_(2) has excellent stability for more than 100 h at an initial current density of 100 mA cm^(-2).

Scalable solid-phase synthesis of defect-rich graphene for oxygen reduction electrocatalysis

Defect-engineered carbon materials have been emerged as promising electrocatalysts for oxygen reduction reaction(ORR)in metal-air batteries.Developing a facile strategy for the preparation of highly active nanocarbon electrocatalysts remains challenging.Herein,a low-cost and simple route is developed to synthesize defective graphene by pyrolyzing the mixture of glucose and carbon nitride.Molecular dynamics simulations reveal that the graphene formation is ascribed to two-dimensional layered feature of carbon nitride,and high compatibility of carbon nitride/glucose systems.Structural measurements suggest that the graphene possesses rich edge and topological defects.The graphene catalyst exhibits higher power density than commercial Pt/C catalyst in a primary Zn-air battery.Combining experimental results and theoretical thermodynamic analysis,it is identified that graphitic nitrogen-modified topological defects at carbon framework edges are responsible for the decent ORR performance.The strategy presented in this work can be can be scaled up readily to fabricate defective carbon materials.

Mechanochemical Reaction of Lanthanum Carbonate with Sodium Hydroxide and Preparation of Lanthanum Oxide Nanoparticle

The preparation of nano sized La 2O 3 powder by mechanochemical reaction of lanthanum carbonate with sodium hydroxide and subsequent heat treatment was studied using X ray diffraction, differential thermal and thermo gravimetric analysis and transmission electron microscopy. It was found that the mechanochemical reaction process can be divided into two steps: the first step is the multi phases mechanochemical reaction of lanthanum carbonate with NaOH to form amorphous lanthanum basic carbonate and lanthanum hydroxide, and the second step is the crystallization of basic lanthanum carbonate with the formula of La 2(OH) 2(CO 3) 2·H 2O under a quasi hydrothermal synthesis condition caused by the mechanical ball milling. The synthesized La 2O 3 powder appears clearly separated spherical like monodisperse nano size particles in which particle size ranges from 30 to 50 nm.

Preparation of Lead-free Base Glaze Suitable for Pearlescent Pigments by Low-temperature Solid-phase Reaction with Alkali Waste

A lead-free base glaze suitable for pearlescent pigments was prepared by a low-temperature solid-phase reaction with alkali waste.Tests were performed to evaluate the effects of the sintering conditions and alkali waste composition on the prepared base glaze and pearlescent glaze.The experimental results show that partially replacing SiO_(2) with B_(2)O_(3) effectively reduced the sintering temperature and time to form a glass network,but the network structure becomes disconnected as the B_(2)O_(3) content increases.An amorphous base glaze was obtained when soda ash was replaced with a small amount of alkali waste,but increasing the addition of NaCl further was adverse to base glaze formation by resulting in crystallization of the base glaze and a decrease in the bridging oxygen content.The pearlescent pigment was thermally stable in the glaze at 750℃,while higher temperatures caused the crystalline phase of NaAlSiO_(4) to appear and adhere to the surface of pigment granules,which degraded the pearlescent effect of the glaze.

Use of Magic Angle Spinning ~1H NMR Spectroscopy to Monitor Reactions in Solid-Phase Synthesis

Proton NMR-spectra of Wang resin bound compounds were obtained using the magic angle spinning 1HNMR technique with standard equipment. It was possible to analyse the spectra to evaluate their utility in solid-phase chernistry. A typical example was presented, which could directly monitor solid-phase reactions

Mechanochemical Reaction of Aromatic Ketones and Aldehydes in the Presence of Zn-ZnCl_2

The solvent-free reactions of aromatic ketones and aldehydes in the presence of Zn-ZnCl2 were performed with the aid of high-speed vibration mill, Retsch MM200 mixer mill and Retsch RM100 mortar grinder to give pinacol coupling and reduction products in varying yields.

Stochastic Four-State Mechanochemical Model of F_1-ATPase

F_1-ATPase, a part of ATP synthase, can synthesize and hydrolyze ATP moleculars in which the centralγ-subunit rotates inside the α_3β_3 cylinder.A stochastic four-state mechanochemical coupling model of F_1-ATPase isstudied with the aid of the master equation.In this model, the ATP hydrolysis and synthesis are dependent on ATP,ADP, and Pi concentrations.The effects of ATP concentration, ADP concentration, and the external torque on theoccupation probability of binding-state, the rotation rate and the diffusion coefficient of F_1-ATPase are investigated.Moreover, the results from this model are compared with experiments.The mechanochemical mechanism F_1-ATPase isqualitatively explained by the model.

Effect of Annealing Temperature and Atmosphere to Surface Solid Phase Reaction of Sapphire Substrates and Spin-Coated Copper Nitrate Gel Films

The solid-phase reaction of sapphire (Al2O3) substrates and spin-coated copper nitrate films was studied. X-ray diffraction analysis revealed that a CuO fraction was observed by annealing at temperatures higher than 800℃. In addition, crystalline CuAlO2 was formed at annealing temperatures in the range of 900℃ – 1000℃ by solid-phase reaction of the spin-coated films and sapphire substrate. Crystalline CuAlO2 was formed by annealing at 1000℃ for 5 - 10 h, and CuAl2O4 was formed by annealing at 1000℃ for 15 h. When annealing under N2 flow, Cu2O was observed rather than CuAlO2. For a sample annealed in air at 1000℃ for 5 h, X-ray photoelectron spectroscopy measurements at various depths from surface revealed that Cu2+ ions are located around the surface, which suggests that the CuO fraction is present near the surface while the CuAlO2 fraction is located at greater depths from the surface of the samples. The depth profile of the sample suggests that there is no pure CuAlO2 layer in the sample, but that crystalline CuAlO2 is present in the sample as a mixture with CuO and Al2O3.

Preparation for intermetallic powders of Cu-Sn and Cu-Ni-Sn systems via solid-liquid reaction milling technique

The Cu-Sn binary intermetallic powders were obtained via a patented reaction ball milling technique. The Sn melt reacted with the solid-state Cu during the milling process at different temperatures for different intervals. Two kinds of binary intermetallics were obtained. For 12 h,Cu6Sn5 was prepared by milling Sn melt at 573 K while Cu3Sn by milling Sn melt at 773 K. And a mixture of Cu6Sn5 and Cu3Sn was fabricated at 673 K. All these intermetallic powders had mean grain sizes of less than 100 nm. A finer microstructure was obtained by milling Sn melt blended with 20%(mass fraction) Ni powders at 573 K for 12 h. The reaction mechanism and advantages were discussed in comparison with that of high-energy ball milling. The results show the solutionizing of Ni powders in the Cu6Sn5 intermetallic.

A high-loading and cycle-stable solid-phase conversion sulfur cathode using edible fungus slag-derived microporous carbon as sulfur host

Developing a high sulfur(S)-loading cathode with high capacity utilization and long term cyclability is a key challenge for commercial implementation of Li-S battery technology.To overcome this challenge,we propose a solid-phase conversion sulfur cathode by using an edible fungus slag-derived porous carbon(CFS)as sulfur host to fabricate the S/CFS composite and meanwhile,utilizing the vinyl carbonate(VC)as co-solvent of the ether-based electrolyte to in-situ form a protective layer on the S/CFS composite surface through its nucleophilic reaction with the freshly generated lithium polysulfides(LiPSs)at the very beginning of initial discharge,thus isolating the interior sulfur from the outer electrolyte and inhibiting the further generation of soluble LiPSs.Benefitting from the ultrahigh specific surface area of>3,000 m^(2)·g^(−1),ideal pore size of<4 nm,and large pore volume of>2.0 cm^(3)·g^(−1)of the CFS host matrix,the S/CFS cathode even with a high S-loading of 80 wt.%(based on the weight of S/CFS composite)can still operate in a solid-phase conversion manner in the VC-ether co-solvent electrolyte to exhibit a high reversible capacity of 1,557 mAh·g^(−1),a high rate capability with 50%remaining capacity at 2 A·g^(−1)and a high cycling efficiency of 99.9%over 500 cycles.The results presented in this work suggest that a combined action of solid-phase conversion electrochemistry and nanoarchitectured host structure may provide a new path for the design and development of practical lithium-sulfur batteries.

单分散球形超细氧化铈的机械化学反应制备法

采用湿固相机械化学反应法制备单分散球形超细氧化铈粉体 ,化学分析和XRD物相分析结果表明球磨作用不仅改善了反应的热力学和动力学条件 ,使反应能在较短的时间内完成 ,而且还促进了产物的结晶化 ,得到了结晶性良好的新物相 ,有利于球磨产物的后续处理。随着球磨反应的进行 ,颗粒粒度减小 ,直至亚微米级时球磨反应使颗粒的减小趋势与晶粒生长导致颗粒长大的趋势达到平衡 ,粒度降低幅度减小。球磨产物在后续煅烧过程中 ,其粒度随温度的升高是先减小而后增大 ,但在 10 5 0℃之前的增大不够明显。XRD、粒度分布及扫描电镜分析结果表明煅烧产物为球形的单分散的超细氧化铈。

机械力化学技术研究进展

金属和无机非金属粉末在高能球磨过程中受到强烈的机械力作用 ,组织不断细加、内部缺陷不断增加 ,导致材料体系自由能大幅度提高 ,在球与粉末颗粒碰撞的瞬间可以诱发固 固、固 液和固 气态化学反应。利用这种工艺被称之为机械力化学 ,可广泛用于制备纳米晶材料、复合纳米材料、纳米粒子、弥散强化材料、高分子聚合物以及进行矿物、废物处理和金属精炼。深入讨论了机械力化学过程的原理、特点及其应用。

机械化学法制备N掺杂纳米TiO_2可见光光催化剂及其性能研究

以锐钛矿型TiO2为原料,HMT(六亚甲基四胺)为掺杂N源,采用机械化学法经过600 r.min-1×2 h高能球磨,后续以焙烧处理,合成了N掺杂纳米TiO2粉末。所制备的粉末为锐钛矿、金红石和板钛矿的混合相,对波长大于400 nm的可见光具有良好的吸收性能,其吸收边红移至530 nm;在λ>400 nm的可见光照射下,HMT加入量为10%的样品对甲基蓝的降解率比原料粉末提高了2.7倍。

机械力固相化学反应法合成稀土磷酸盐绿色荧光粉

以CeCl3·7H2O,La(NO3)3·6H2O,Tb(NO3)3·6H2O,(NH4)2HPO4和适量表面活性剂为原料,采用机械力固相化学反应法制备磷酸盐绿色荧光粉,用XRD和TG DTA分析技术,研究球磨过程和煅烧过程中的物相变化,用扫描电镜和粒度分析对材料的形貌、粒径进行表征。用荧光光谱分析样品的发光性能。研究结果表明,随着球磨时间的增加,有助于产物的晶化,但其结晶程度较低,煅烧后则形成晶型完整的稀土正磷酸盐荧光粉,所得样品为亚微米级的球型绿色荧光粉,在272nm紫外线激发下发绿色荧光,发射主峰在548nm。

机械化学法合成纳米ZnO粉体

利用机械化学法合成了单相ZnO粉体,XRD分析结果表明,ZnSO_4/NaOH(mol比)在1/2.1～1/3.0之间均可合成ZnO粒子,ZnO产率在ZnSO_4/NaOH为1/2.5时最大,TEM分析表明,ZnO粒子的粒径在40～80nm范围,对于反应机理,认为是固-固反应中放出的大量的热,使Zn(OH)_2直接转化为ZnO粒子,光吸收性能表明,纳米ZnO粉体的紫外吸收性能(200～400nm)较普通ZnO粉体强得多。

Al-TiO_2-B_2O_3反应体系的机械力化学与热化学行为

通过机械球磨系统地研究Al-TiO2-B2O3反应体系粉体的机械力化学与热化学行为。结果表明:Al-TiO2-B2O3复合粉体球磨20h后,中位径可达到4.35μm,形状近乎球形,并生成少量Al2O3、TiB2等新相;机械力化学作用使其在400℃左右就可发生缓慢的固相反应,在670℃时反应最为剧烈;在700℃热处理时,产物大部分为Al2O3和TiB2;在1000℃热处理时,产物全部为Al2O3和TiB2。

机械合金化Cu-C-Ti复合粉末的组织特征

采用扫描电镜、X射线衍射分析等实验手段 ,研究了Cu 2 %C 8%Ti(质量分数 )混合粉末在机械合金化 (MA)时的组织形态特征以及微观结构的变化规律。结果表明 ,Cu C Ti混合粉末经 48hMA后形成了Cu基过饱和固溶体 ;96hMA后 ,部分Ti、C溶质元素脱溶析出并且发生机械化学反应而生成碳化物TiC。MA导致复合粉末细化与扁平化 ,自由表面、晶界、亚晶界以及位错等晶体缺陷的急剧增加而明显地降低了扩散激活能 ,它是形成过饱和固溶体和促进第二相析出的主要原因。

机械化学反应法制备纳米晶TaC和TaSi_2

采用ＸＲＤ，ＴＥＭ和ＳＥＭ研究了用机械化学反应法制备金属间化合物ＴａＣ和ＴａＳｉ２时的结构演变．结果表明：ＴａＣ和ＴａＳｉ２是通过互扩散由元素直接反应合成的，高能球磨引入的高密度缺陷和纳米界面大大促进了这一反应过程．

纳米铌镁酸铅机械化学法低温快速合成

采用一种新型螺杆研磨机,以氧化物为原料,仅需3h的研磨,即可得到钙钛矿相结构的纳米铌镁酸铅(PMN)粉体.并研究了原料粉质量、研磨功率、研磨时间等不同因素对于合成的影响.通过对比分析发现,提高研磨功率,可以缩短合成时间、提高产物纯度、减小粉体粒径.通过原料交叉反应实验,确定剪切力机械化学法合成铌镁酸铅的反应机理为:MgO与Nb2O5反应生成MgNb2O6,然后与PbO反应获得铌镁酸铅.