Tribological performance of binderless tungsten carbide reinforced by multilayer graphene and SiC whisker

Binderless tungsten carbides (BTC) have attracted the attention of both academia and industry due to their excellent hardness, high-temperature strength as well as corrosion resistance. Herein, a set of binderless WC-based composites were developed employing two-step spark plasma sintering. The mechanical response together with tribological performance was investigated as a function of various reinforcements including SiC whisker (SiC_w) and multilayer graphene (MLG). The results suggested that the coupling and synergy of MLG and SiC_w played a critical role in microstructure refinement and homogenization, consequently advancing the mechanical and tribological properties of BTC. The MLG-SiC_w/BTC displayed the optimal comprehensive performances, and the associated toughening and anti-friction mechanisms were determined and analyzed. Such material design offers an effective approach to enhance the mechanical and tribological responses of ceramic materials.     

碳化钨载铂的制备及其对硝基苯的电催化还原

以偏钨酸铵（AMT）为钨源前驱体,气流式喷雾干燥仪造粒,得到空心球状结构偏钨酸铵,固定床气固反应,以CO/CO₂为还原碳化气氛在800℃下制备了介孔空心球状碳化钨。采用氯铂酸作为铂源,用浸渍、气相还原法制备了Pt/WC粉末催化剂。通过XRD和SEM测试手段对Pt/WC粉末样品进行了表征,表明Pt成功负载在介孔WC材料上。采用循环伏安法、以Pt/WC粉末微电极为工作电极,研究了Pt/WC对在质子惰性介质中硝基苯的硝基还原的催化作用。结果表明,Pt/WC催化剂对硝基还原有着良好的电催化活性和化学稳定性。     

超细碳化钨制备过程及机理研究进展

超细碳化钨（WC）具有硬度高、耐磨性好、强度高和韧性较高的特点,是制备硬质合金最基础的原料。因此,超细碳化钨的制备成为学术界和工业界关注的焦点,也是硬质合金制备领域研究的重点。从反应体系的角度综述了超细碳化钨粉体制备技术,对相关反应路径机理进行了分析,并展望了超细碳化钨制备技术的发展趋势。     

Catalytic activity and XPS surface determination of tungsten carbide for hydrocarbon reforming. Influence of the oxygen

The influence of oxygen on the catalytic properties of tungsten carbide has been studied for the reforming reaction of 2-methylpentane in a great excess of hydrogen . The oxygen surface concentration has been measured by the ratio of the signal area of the O_1s and the W_4f levels as determined by X-ray photoelectron spectroscopy. Two kinds of processes are observed: cracking and isomerization reactions. The introduction of oxygen at T=350°C leads to a deep decrease of the cracking reaction kinetics; about two orders of magnitude. The tungsten carbide, strongly selective for cracking reactions in absence of oxygen, becomes very selective for isomer production in the presence of oxygen.     

电催化氮气还原合成氨催化材料研究进展

氨是纺织、制药、化肥等领域重要的化工原料,也是一种清洁的能源载体,需求量大。目前氨的工业生产主要为Haber-Bosch法,反应条件严苛,能源消耗大且碳排放较高。电催化氮气还原(NRR)合成氨是一种在常温常压下进行的反应,工作电位低,且电能可通过清洁能源提供,是一种很有潜力的合成氨新工艺。但目前电催化NRR材料的产氨速率和法拉第效率低、工作稳定性不够高、溶液中痕量氨的定量检测困难及检测标准不统一等都为其发展带来了巨大挑战。本文首先介绍了电催化NRR的反应机理和常用研究方法,然后重点梳理了2019年以来NRR催化材料的最新研究进展,最后对该领域研究面临的挑战和机遇进行了展望。     

碳纳米管、碳化钨在直接法合成过氧化氢中的应用

选用新型纳米材料——碳纳米管（CNTs）作为催化剂载体,用沉积沉淀法制备负载型钯-铂合金催化剂。同时选用过渡金属碳化物材料（碳化钨）为催化剂,其具有类似于Pt的表面电子结构,有望替代贵金属催化剂。探讨了Pd-Pt/CNTs及碳化钨在氢氧直接合成过氧化氢反应中的催化性能。     

Electrocatalytic activity of nitrogen doped carbon nanotubes with different morphologies for oxygen reduction reaction

Nitrogen doped carbon nanotubes (NCNTs) were synthesized by a single step chemical vapor deposition technique using either ferrocene or iron(II) phthalocyanine as catalyst and pyridine as the carbon and nitrogen precursor. Variations in surface morphology and electrocatalytic activity for oxygen reduction reaction (ORR) were observed between the NCNTs synthesized using different catalysts. The structural and chemical characterizations were carried out using transmission electron microscopy (TEM), Raman spectroscopy and X-ray photoelectron spectroscopy (XPS). The electrochemical activity of NCNTs was evaluated with rotating ring disc electrode (RRDE) voltammetry. Structural characterization suggested more defects formed on the NCNTs synthesized from ferrocene (Fc-NCNTs) which led to a rugged surface morphology compared to the NCNTs synthesized from iron(II) phthalocyanine (FePc-NCNTs). Based on the RRDE voltammetry study, Fc-NCNTs demonstrated much higher activity for ORR than FePc-NCNT. Evidences from the structural and chemical characterizations illustrate the potential impact of catalyst structure in shaping the surface structure of NCNTs and the positive effect of surface defects on ORR activity. These results showed that potential improvements on ORR activity of NCNTs could be achieved by tailoring the surface structure of NCNTs by using catalysts with different structures.     

碳化钨纳米晶薄膜电极的制备及其对甲醇电氧化性能

引　言碳化钨具有与金属铂相类似的表面电子结构[1], 因此, 人们一直在探索碳化钨在化学领域中的催化性能, 期望利用矿藏丰富、价格低廉的钨矿优势, 用碳化钨来替代资源稀缺、价格昂贵的铂及铂基合金催化剂. 研究表明, 碳化钨在烷烃重整、异构化反应以及在氢析出反应等方面具有     

Kinetics of reaction of low concentration mixtures of oxides of nitrogen,ammonia and water vapour

The kinetics of reaction between oxides of nitrogen, ammonia, water vapour and oxygen in ppm quantities in nitrogen were studied. The kinetics of the nitrogen dioxide-ammonia reaction and of the nitrogen dioxide-water reaction were investigated separately, and a reaction model was developed to predict the rate of disappearance of nitrogen dioxide in the overall reaction system based on the reaction rate expressions deduced for the separate reactions. There was satisfactory agreement between measured and predicted dioxide concentrations as a function of time. The results have relevance to consideration of clean-up processes of tail gases in nitric acid plants and to studies of reactions in polluted atmospheres.     

Stability and electrocatalytic activity for oxygen reduction in WC + Ta catalyst

Tantalum (Ta)-added tungsten carbide (WC) (WC+Ta) was examined in order to obtain surperior characteristics in stability and electrocatalytic activity for the oxygen reduction reaction (ORR) in acid electrolyte. The stability and the electrocatalytic activity of the WC+Ta catalyst were electrochemically investigated and compared to the pure WC. It was proved that the stability of the tungsten carbide was significantly increased by the addition of tantalum compared to the pure WC. The enhanced stability might be due to the formation of the W-Ta alloy in the WC+Ta catalyst. The reduction current of the WC+Ta catalyst for the ORR was observed at a potential of 0.8 V (versus dynamin hydrogen eletrode (DHE)) or less noble potential. This value was about 0.35 V higher than that of the pure WC. The enhanced electrocatalytic activity for the ORR might be caused by the presence of tungsten carbide, which exists on the surface and/or sub-surface.     

非球面玻璃模造用碳化钨模仁磁控溅射铼-铱镀膜工艺优化

通过钽过渡镀层与铼-铱复合镀层相结合的膜层结构,解决了非球面玻璃模造碳化钨模仁热压寿命短、沾黏等问题。通过离子源和镀膜层厚度参数的优化调整,得到了最佳镀膜工艺和参数,改善了模仁的表面品质,延长了模仁的使用寿命。镀钽膜层15min及铼-铱膜层21min后所得镀膜的总厚度约为270nm,模仁热压寿命可超过3000次。     

The effect of substrate temperature on microstructural evolution and hardenability of tungsten carbide coating in hot filament chemical vapor deposition

Effect of substrate temperature on microstructural evolution and hardenability of tungsten carbide coating produced by hot filament chemical vapor deposition (HFCVD) process was studied. Annealed sheets of 316L stainless steels were used as the substrate. HFCVD technique, with substrate temperatures of 400 and 500°C, was used to deposit tungsten carbide coating on these sheets. Field Emission Scanning Electron Microscope (FE‐SEM) was used to study the evolution of microstructure. X‐Ray Diffraction spectroscopy was used to analyze the phases formed and Raman spectroscopy was employed to differentiate molecular composition of the coatings. The amount of the porosity of the coatings was measured and Vickers hardness measurement was used for hardness assessment. Results show that the tungsten carbide coatings have a honeycomb structure and increasing the temperature of the substrate increases the amount of porosity of the coating. XRD results showed that 3 different crystalline structures containing W, WC, and W₂C were formed in the coating deposited on the 316L stainless steel. Increasing the temperature of the deposition has increased the intensity of the peaks in the XRD results. Raman spectroscopy results indicated the presence of a carbon in the tungsten carbide coatings. Finally, microhardness of the tungsten carbide coating increases with increasing the temperature of the substrate.     

Facile and flexible fabrication of structured array surfaces on binderless tungsten carbide by using electrical discharge machining with a novel self-assembly ball electrode

Electrical discharge machining (EDM) method is an innovative method for the fabrication of structured array surfaces on binderless tungsten carbide (WC) which is a typical embossing mold material, compared to traditional machining methods. To improve the convenience of electrode replacement and the fabrication efficiency of the structured array, a novel self-assembly ball electrode is innovatively developed. The feasibility of machining binderless WC with a self-assembly ball electrode was studied and its effect on profile deviation analyzed. Furthermore, the discharge condition's effect on surface roughness, material removal rate (MRR), and tool wear ratio (TWR) was investigated. The microstructure, phase structure, and element distribution of binderless WC caused by EDM were characterized by Raman spectroscopy, scanning electron microscopy, and energy dispersive x-ray spectroscopy. The results indicated that the maximum profile deviation of the different random structured arrays was about 3.7 μm. The surface roughness of all structured arrays was below 1 μm. The maximum TWR was about 0.008 mm³/min. Besides, the binderless WC surface after EDM presented strong D and G carbon peaks, which means the precipitation and transformation of the WC phase during the discharge process. Finally, different kinds of self-assembly ball electrodes are developed and used to fabricate the lens array structures on binderless WC. The fast fabrication of the micro-lens array surfaces in different arrangements sheds some light on the design and manufacturing of other functional structured surfaces.     

Sonochemical synthesis of tungsten carbide-palladium nanocomposites and their electrocatalytic activity for hydrogen oxidation reaction

Nanocomposites between β-WC and Pd nanoparticles supported on carbon are synthesized and their electrocatalytic properties for the hydrogen oxidation reaction have been investigated. The Pd nanoparticles are obtained by a chemical reduction reaction of PdCl₂ and the β-WC nanoparticles by a sonochemical decomposition of W(CO)₆ on Pd-loaded carbon followed by heat-treatment. Depending on the relative amounts of W to Pd, the Pd nanoparticles can be reacted with W to form Pd-W alloy nanoparticles. The Pd-W alloy, whose composition is estimated to have W less than 18 at.% based on its lattice parameter, lost most of the catalytic activity of Pd. On the other hand, the nanocomposite between β-WC and pure Pd shows an enhanced activity compared with that of Pd nanoparticles alone. This enhancement can be explained with the H⁺-spill-over to β-WC.     

氧化石墨烯和过渡金属碳/氮化合物固定化酶

二维纳米材料具有高机械强度和比表面积、大量表面官能团、良好的亲水性及生物相容性,是固定化酶的良好载体。本文选取经典的氧化石墨烯（GO）以及新型的过渡金属碳/氮化合物（MXenes）,分别介绍了它们的制备方法和结构、物理和化学性质,综述了它们在固定化酶领域的应用研究,并进行了比较。文中指出：GO由石墨烯经化学氧化再剥离制得,MXenes由其前体经刻蚀制得,不同的氧化或刻蚀方法制得的材料在组成、结构、性能等方面存在差异。GO表面的可反应官能团更多,包括羟基、羧基和环氧基,故在固定化酶领域应用广泛。MXenes固定化酶则主要利用表面的羟基反应或负电荷吸附,目前主要用于制备生物传感器。最后指出这两种材料还存在制备效率低、纳米片易聚集、循环利用性差等问题。今后的发展方向是要开发更为简单和安全的材料制备方法,探索更为有效的插层和剥离手段以及改善固定化酶的回收策略,进一步推进二维纳米材料在固定化酶领域的应用。     

A study of nitrogen and carbon dioxide chemisorption on platinum black

The relationship between sites responsible for nitrogen chemisorption and sites responsible for stronger adsorption of carbon dioxide on platinum black is reported. A 2 to 1 ratio has been found between molecules of more strongly adsorbed carbon dioxide and molecules of nitrogen chemisorbed on individual samples. This relationship has allowed us to deduce the structure of chemisorbed carbon dioxide. Carbon dioxide is relatively weakly chemisorbed on platinum. Reasons for the weakness of this chemisorption are discussed.     

光（电）催化氮气还原合成氨研究进展

光（电）催化氮气还原技术利用天然太阳能作为能源,具有成本低、反应条件温和等众多优势,可解决传统工业合成氨Haber-Bosch工艺的高能耗以及高CO₂排放等问题,被认为是目前最具前景的新兴合成氨技术之一。由于氮气为非极性分子,在水中溶解度极低,且本身呈现化学惰性,难以被活化,使得整体的氮气还原转化合成氨效率较低。同时,光生载流子的利用率也显著影响整体的催化效率。为此,光（电）催化氮气还原技术的关键在于催化剂的设计和催化反应体系的优化。本文在介绍光（电）催化氮气还原合成氨反应过程以及机理的基础上,主要从促进氮气溶解扩散、氮气吸附和活化以及强化载流子分离和传输等具体反应过程出发,重点综述近期国内外在光（电）催化氮气还原合成氨领域基于上述反应过程强化的最新研究现状。最后,指出了目前光（电）催化氮气还原合成氨研究领域面临的挑战,并对此领域的未来发展趋势进行了分析与展望。     

氧化石墨烯生长钨基氧化物酸环境电催化析氢

为了解决商用铂碳电极在电催化析氢反应（HER）领域生产成本高、催化剂使用周期短等问题,利用磷钨酸提供钨源,以单层氧化石墨烯（GO）作为载体,引入利于电子传输轨道的碳纳米管（CNTs）,通过一步水热法和空气中煅烧制备得到WO3-rGO-CNTs纳米异质结电催化剂。利用FT-IR、XRD、XPS、TG、SEM、EDAX、TEM和BET对WO3-rGO-CNTs的化学结构和物理形貌进行了表征。结果表明,在单层GO表面均匀生长WO3晶体,并引入CNTs后,纳米异质结WO3-rGO-CNTs在酸性电解质中表现出优异的HER催化活性。利用线性伏安法（LSV）和循环伏安法（CV）对WO3-rGO-CNTs进行HER测试,当电流密度为10 mA/cm2时,其过电势为218 mV;塔菲尔斜率为130.5 mV/dec。当过电势为-0.5 V vs. RHE时,其阻抗值为8.2 Ω。同时,WO3-rGO-CNTs纳米异质结可以在218 mV（电流密度为10 mA/cm2）过电势下,保持50 h的稳定性和耐久性;其双层电容值为1.2 mF/cm2。电化学数据表明,WO3与GO和CNTs间由于异质结构的存在,产生了协同效应：GO为WO3晶体提供了广阔的金属反应活性位点,而CNTs则提供了利于电子传输的活性轨道。     

基于氮掺杂碳量子点的荧光微球制备和Fe3+检测

分别以尿素、氨水、二乙烯三胺、多乙烯多胺为氮源,绿色廉价的白菜为碳源,采用水热法合成氮掺杂的蓝色荧光碳量子点,结果表明多乙烯多胺氮掺杂碳量子点（NCDs）荧光量子产率最高为53.3%。然后将NCDs作为荧光探针应用于荧光微球制备和Fe³⁺检测方面,以三聚氰胺甲醛（MF）为载体,合成了氨基化MF荧光微球;基于Fe³⁺对NCDs良好的荧光猝灭效应,建立了一种荧光测定Fe³⁺的方法,并对NCDs和MF荧光微球的结构和性能进行表征。结果表明,NCDs的荧光性能得到了显著的改善;MF荧光微球单分散性好、荧光性能好且稳定,在生物医学领域方面有重要的应用价值;NCDs对Fe³⁺具有单一选择性,Fe³⁺浓度在0~2μmol/L内与NCDs的荧光猝灭程度呈良好的线性关系（R²=0.9945）,检出限为0.035μmol/L。将该体系应用于实际水样中Fe³⁺的测定,相对标准偏差（RSD,n=6）在1.42%~3.02%内,加标回收率在98.7%~104.5%之间。该体系对Fe³⁺检测灵敏性好、选择性高以及抗干扰性强,在离子分析检测方面有潜在的应用前景。     

氮掺杂石墨烯/多孔碳复合材料的制备及其氧还原催化性能

采用简单、无模板的方法制备了氮掺杂多孔石墨烯/碳复合材料(NPGC)。采用SEM、XRD、Raman、XPS等分析手段对NPGC的形貌、组成以及结构进行了表征，利用旋转圆盘电极技术测试了其电催化氧还原反应(ORR)活性。结果表明，葡萄糖在水热后生成的碳与石墨烯成功复合，并在950℃炭化、活化后形成了相互渗透、结构良好的三维片状多孔网络结构；其氮含量高达9.47%。NPGC作为一种高效的非金属ORR电催化剂，在碱性溶液中具有较高的起始电位[0.87 V(vs RHE)]和较大的极限电流密度(4.7 mA?cm^?2)，以及其ORR平均转移电子数为3.8。与商业Pt/C催化剂相比，NPGC具有较强的耐甲醇性和长期耐久性，且制备成本较低，具有广阔的应用前景。