Fabrication of novel ZnTe-based photocatalyst: Synergistic effect of dye sensitization and bridge engineering for boosting hydrogen evolution over ZnTe

Herein, a novel ZnTe-based photocatalyst is successfully synthesized via a facile combination of water-bath and hydrothermal processes. Morphology characterization and X-ray diffraction analysis reveal that ZnTe presents irregular granular shape and cubic crystal structure. Moreover, Mott-Schottky measurement shows that the conduction band potential of ZnTe is ?0.84 V (vs NHE). With Eosin Y (EY) sensitization, ZnTe exhibits superior photocatalytic hydrogen evolution activity (223.5 μmol g^?1 h^?1). Meanwhile, WC-ZnTe heterojunction is constructed by depositing ZnTe nanoparticles on bulk WC and obtains the optimal H₂ generation rate (559.1 μmol g^?1 h^?1) under EY sensitization. Electrochemical and photoluminescence results further prove that WC as electron bridge could reduce the interfacial resistance and suppress e^?-h⁺ pairs recombination. This study explores the potential application of ZnTe as a newly active photocatalyst in photocatalytic water splitting, and emphasizes the synergistic effect of dye sensitization and bridge engineering.     

Ultrafine porous boron nitride nanofiber-toughened WC composites

Porous fibers are widely used in catalysis chemistry and hydrogen storage but are rarely used in structural ceramics. In this study, spark plasma sintering was used to prepare an ultrafine porous boron nitride nanofiber-toughened WC composite for the first time. The obtained WC-0.05 wt% ultrafine porous boron nitride nanofiber composites exhibited better properties (ie, a 2.3% increase in hardness and a 19.6% increase in fracture toughness) compared to those of the pure WC specimen. The fiber porosity improved the second phase-WC matrix microstructural combination. The described approach is a novel preparation method for the WC composites. Furthermore, a new toughening mechanism, which is based on “pinning and stretching”, was determined. These findings suggest that porous boron nitride fibers can be considered to be second phases for toughening the WC composites.     

Mechanism of methanol decomposition on the Pd/WC(0001) surface unveiled by first-principles calculations

In this study, the decomposition of methanol into the CO and H species on the Pd/tungsten carbide (WC)(0001) surface is systematically investigated using periodic density functional theory (DFT) calculations. The possible reaction pathways and intermediates are determined. The results reveal that saturated molecules, i.e., methanol and formaldehyde, adsorb weakly on the Pd/ WC(0001) surface. Both CO and H prefer three-fold sites, with adsorption energies of −1.51 and −2.67 eV, respectively. On the other hand, CH₃O stably binds at three-fold and bridge sites, with an adsorption energy of −2.58 eV. However, most of the other intermediates tend to adsorb to the surface with the carbon and oxygen atoms in their sp³ and hydroxyl-like configurations, respectively. Hence, the C atom of CH₂OH preferentially attaches to the top sites, CHOH and CH₂O adsorb at the bridge sites, while COH and CHO occupy the three-fold sites. The DFT calculations indicate that the rupture of the initial C–H bond promotes the decomposition of CH₃OH and CH₂OH, whereas in the case of CHOH, O–H bond scission is favored over the C–H bond rupture. Thus, the most probable methanol decomposition pathway on the Pd/WC(0001) surface is CH₃OH → CH₂OH → trans-CHOH → CHO → CO. The present study demonstrates that the synergistic effect of WC (as carrier) and Pd (as catalyst) alters the CH₃OH decomposition pathway and reduces the noble metal utilization.     

WC涂层纳米划痕过程中摩擦学性能及演化特征的分子动力学研究

为研究纳米划擦过程中WC涂层纳米级摩擦演化特征,利用大型原子/分子大规模并行模拟器建立了不同条件（载荷、划痕深度、划痕速度）下的分子动力学模拟模型。结果表明：摩擦力和摩擦系数随着划痕深度的增加而增大;当压头划擦试样时,沿划痕方向在压头前方及凹槽两侧的原子被挤压、剪切、堆积。瞬时摩擦曲线在初始阶段和稳定阶段表现出明显的摩擦学特征,摩擦过程中压头下方区域晶体出现错位、滑移、间隙或空位。随着划痕速度的增加,体系应变能超过原子间相互约束,原子突破约束,在划痕沟槽两侧堆积,堆积的表面形貌和外缘变得粗糙,亚表面晶体结构产生缺陷。本研究有助于在纳米尺度了解WC涂层摩擦过程的微观磨损机理。     

WC含量对激光熔覆NiCrBSi-WC复合涂层显微结构及力学性能的影响

目的 为盾构、勘探及采矿等高载荷严苛磨损条件下的构件表面防护提供一种新的涂层方法。方法 以激光熔覆技术为手段,在NiCrBSi粉末中混入30%~80%（体积分数）的球形WC颗粒,用以制备NiCrBSi-WC复合涂层。研究了WC颗粒含量对涂层显微组织形成、硬度、断裂韧性和耐磨性的影响规律。采用SEM分析了涂层的显微组织;通过显微维氏硬度计测试涂层的硬度;通过压痕法测试涂层的断裂韧性;采用磨粒磨损试验表征涂层的耐磨性。结果 当WC颗粒体积分数低于60%时,熔融金属的黏度较低,密度更大的WC颗粒会沉淀,导致涂层表层的WC颗粒含量较低;当WC颗粒体积分数介于60%~80%时,WC颗粒在涂层内均匀分布,涂层内无气孔及裂纹等缺陷。当WC颗粒体积分数达到80%时,熔体黏度过大,使气体难以及时逸出,在涂层内形成大量气孔。随着WC体积分数由30%上升到80%时,涂层的平均硬度由67HRC提高到85HRC。涂层的断裂韧性随WC含量的提高,出现先升高后下降的反常现象。60%WC含量的复合涂层表现出最佳的耐磨性,比滚刀常用材料H13钢提高约9倍。结论 采用常规激光熔覆技术时,添加40%~60%范围内的硬质陶瓷颗粒,可获得硬质颗粒分布均匀且耐磨性与抗冲击性能优异的复合涂层。     

WC晶体结构特征对HVOF喷涂纳米结构WC-CoCr涂层组织及性能的影响

为提高纳米结构WC-CoCr涂层的综合力学性能,采用超音速火焰喷涂（HVOF）工艺制备纳米结构和超细结构WC-CoCr涂层。探讨了不同晶体特征的WC粉末对颗粒飞行和沉积变形过程的脱碳行为、涂层微观组织及力学性能的影响。结果表明：含有高密度位错的超细WC粉末在喷涂过程中发生了严重的氧化脱碳,形成了大量的W₂C相,涂层孔隙率较大,断裂韧性显著降低。而含有显著孪晶的纳米WC颗粒具有抑制WC脱碳和增强涂层断裂韧性的作用,纳米结构涂层呈现低脱碳率、高致密性、高硬度和高断裂韧性的优良综合性能。     

Microstructure and properties of WC reinforced Ni-based composite coatings with Y2O3 addition on titanium alloy by laser cladding

ABSTRACT

In this study, WC reinforced Ni-based composite coatings with Y₂O₃ addition were deposited on Ti-6Al-4V titanium substrate by laser cladding. The phases, microstructure, microhardness and wear resistance of the composite coatings were studied by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, microhardness tester and wear tester. The results showed that good metallurgical bonding was achieved between the composite coatings and substrate. The phases mainly were γ-Ni, TiC, TiB₂, Ni₃B, M₂₃C₆ and WC. Most of the WC was dissolved in small pieces of WC during the laser cladding process. The microhardness of the composite coatings was about 3 times that of the titanium substrate and the wear resistance of the composite coatings had a significant increase.     

纳米WC/PTFE镍基复合电刷镀层的摩擦磨损与耐腐蚀性能

针对单一纳米颗粒电刷镀镀层综合性能存在的不足,利用电刷镀技术在45钢基材上制备含纳米WC和PTFE的镍基复合镀层。采用扫描电子显微镜观察电刷镀复合镀层的表面形貌和显微结构,球盘式摩擦磨损试验机测试其干摩擦条件下摩擦磨损性能,在pH=4浓度为0.05mmol/L的硫酸溶液中进行耐腐蚀性试验。结果表明:在镀液中添加不同含量纳米粒子,可以不同程度填补粒子之间的空缺,使镀层表面平整、光滑;含纳米WC和PTFE镍基复合镀层的耐磨损和耐腐蚀性能强于纯镍基镀层和45钢基体,这是由于纳米粒子细晶强化和弥散强化所致;当含1.5g/L纳米WC与7g/L纳米PTFE乳液的复合镀层耐磨损性能最佳;含1g/L纳米WC与5g/L纳米PTFE复合镀层的耐腐蚀性能较纯镍基复合镀层提高一倍;45钢的磨损机制是粘着磨损,纯镍基镀层的磨损机制是剥层磨损,纳米WC/PTFE镍基复合镀层的磨损机制是磨粒磨损。     

超音速喷涂纳米WC复合涂层与电镀铬层的组织及性能

采用超音速火焰喷涂(HVOF)技术和电镀技术分别制备了纳米WC-10Co-4Cr涂层及电镀铬层,通过扫描电镜(SEM)、X射线衍射仪(XRD)、显微硬度计、摩擦磨损试验机、电化学工作站、磨损腐蚀加速试验机等手段对比分析了这两种涂层的性能以及使用寿命。结果表明,纳米WC复合涂层具有远高于电镀铬层的显微硬度、耐磨损性能及结合强度等,并且该涂层具有较高的致密度,而耐腐蚀性能略低于电镀铬层但也远高于基材,磨损腐蚀加速试验结果显示该涂层的使用寿命高达电镀铬层的5倍以上。     

WC粒度对超音速火焰喷涂WC-10Co-4Cr涂层耐腐蚀性能的影响

采用制粒?高温快速烧结法制备两种分别含亚微米级和微米级WC粒径的WC-10Co-4Cr喷涂粉末,并用超音速火焰喷涂(HVOF)技术在45#钢基体上制备涂层;利用扫描电子显微镜和电化学工作站分别对涂层的显微形貌及耐腐蚀性能进行分析检测,探讨WC粒度对涂层耐腐蚀性能的影响和涂层的电化学腐蚀机理。研究结果表明：两种涂层组织致密,界面结合良好;含亚微米级WC粒径的涂层具有相对较低的孔隙率,使其涂层的耐腐蚀性能优于含微米级WC粒径的涂层。在3.5%NaCl溶液中涂层的硬质相WC和粘结相Co发生电偶腐蚀,且低电位的Co相优先腐蚀,导致WC颗粒脱落,出现凹坑及点蚀现象。