Effects of CeO_2 pre-calcined at different temperatures on the performance of Pt/CeO_2–C electrocatalyst for methanol oxidation reaction

Pt/CeO2–C catalysts with CeO_2 pre-calcined at 300–600°C were synthesized by combining hydrothermal calcination and wet impregnation. The effects of the pre-calcined CeO_2 on the performance of Pt/CeO_2–C catalysts in methanol oxidation were investigated. The Pt/CeO2–C catalysts with pre-calcined CeO_2 at 300–600°C showed an average particle size of 2.6–2.9 nm and exhibited better methanol electro-oxidation catalytic activity than the commercial Pt/C catalyst. In specific, the Pt/CeO_2–C catalysts with pre-calcined CeO_2 at 400°C displayed the highest electrochemical surface area value of 68.14 m~2·g~(-1) and If/Ib ratio(the ratio of the forward scanning peak current density(If)and the backward scanning peak current density(Ib)) of 1.26, which are considerably larger than those(53.23 m2·g~(-1) and 0.79, respectively) of the commercial Pt/C catalyst, implying greatly enhanced CO tolerance.     

低氧LiF–NdF3熔盐体系阳极过程的电化学行为研究

The oxidation of oxygen ions and the generation of an anode effect at a low oxygen content of 150 mg/kg were discussed in this paper. Cyclic voltammetry and square-wave voltammetry tests were conducted to explore the anodic processes of LiF–NdF₃ melt after a lengthy period of pre-electrolysis purification at 1000°C (during which the oxygen content reduced from 413 to 150 mg/kg). The oxidation process of oxygen ions was found to have two stages: oxidation product adsorption and CO/CO₂ gas evolution. The adsorption stage was controlled by diffusion, whereas the gas evolution was controlled by the electrochemical reaction. In comparison with oxygen content of 413 mg/kg, the decrease in the amplitude of the current at low oxygen content of 150 mg/kg was much gentler during the forward scanning process when the anode effect occurred. Fluorine-ion oxidation peaks that occurred at about 4.2 V vs. Li/Li+ could be clearly observed in the reverse scanning processes, in which fluorine ions were oxidized and perfluorocarbons were produced, which resulted in an anode effect.     

单斜相SrAl2Si2O8陶瓷的烧结及其对Sr的固化

Monoclinic SrAl₂Si₂O₈ ceramics for Sr immobilization were prepared by a liquid-phase sintering method. The sintering temperature, mineral phase composition, microstructure, flexural strength, bulk density, and Sr ion leaching characteristics of the SrAl₂Si₂O₈ ceramics were investigated. A crystalline monoclinic SrAl₂Si₂O₈ phase formed through liquid-phase sintering at 1223 K. The introduction of four flux agents (B₂O₃, CaO·2B₂O₃, SrO·2B₂O₃, and BaO·2B₂O₃) to the SrAl₂Si₂O₈ ceramics not only reduced the densification temperature and decreased the volatilization of Sr during high-temperature sintering but also impacted the mechanical properties of the ceramics. Product consistency tests showed that the leaching concentration of Sr ions in the sample with flux agent B₂O₃ was the lowest, whereas that of Sr ions in the sample with flux agent BaO·2B₂O₃ was the highest. These results show that the leaching concentration of Sr ions depends largely on the amorphous phase in the ceramics. Meanwhile, the formation of mineral analog ceramics containing Sr is an important factor to improve Sr immobilization.     

气体扩散层集流体对Ni(OH)2纳米结构电化学性能的影响

We report the electrochemical performance of Ni(OH)₂ on a gas diffusion layer (GDL). The Ni(OH)₂ working electrode was successfully prepared via a simple method, and its electrochemical performance in 1 M NaOH electrolyte was investigated. The electrochemical results showed that the Ni(OH)₂/GDL provided the maximum specific capacitance value (418.11 F·g?1) at 1 A·g?1. Furthermore, the Ni(OH)₂ electrode delivered a high specific energy of 17.25 Wh·kg?1 at a specific power of 272.5 W·kg?1 and retained about 81% of the capacitance after 1000 cycles of galvanostatic charge–discharge (GCD) measurements. The results of scanning electron microscopy (SEM) coupled with energy-dispersive X-ray spectroscopy (EDS) revealed the occurrence of sodium deposition after long-time cycling, which caused the reduction in the specific capacitance. This study results suggest that the light-weight GDL, which can help overcome the problem of the oxide layer on metal–foam substrates, is a promising current collector to be used with Ni-based electroactive materials for energy storage applications.     

强耦合非晶态Sb2S3球与碳纳米管中的钠离子和锂离子存储

A facile one-step strategy involving the reaction of antimony chloride with thioacetamide at room temperature is successfully developed for the synthesis of strongly coupled amorphous Sb₂S₃ spheres and carbon nanotubes (CNTs). Benefiting from the unique amorphous structure and its strongly coupled effect with the conductive network of CNTs, this hybrid electrode (Sb₂S₃@CNTs) exhibits remarkable sodium and lithium storage properties with high capacity, good cyclability, and prominent rate capability. For sodium storage, a high capacity of 814 mAh·g?1 at 50 mA·g?1 is delivered by the electrode, and a capacity of 732 mAh·g?1 can still be obtained after 110 cycles. Even up to 2000 mA·g?1, a specific capacity of 584 mAh·g?1 can be achieved. For lithium storage, the electrode exhibits high capacities of 1136 and 704 mAh·g?1 at 100 and 2000 mA·g?1, respectively. Moreover, the cell holds a capacity of 1104 mAh·g?1 under 100 mA·g?1 over 110 cycles. Simple preparation and remarkable electrochemical properties make the Sb₂S₃@CNTs electrode a promising anode for both sodium-ion (SIBs) and lithium-ion batteries (LIBs).     

pH值对β-MnO2颗粒光催化去除银离子的影响

The presence of silver ions (Ag(I)) in wastewater has a detrimental effect on living organisms. Removal of soluble silver, especially at low concentrations, is challenging. This paper presents the use of β-MnO₂ particles as a photocatalyst to remove Ag(I) ions selectively from aqueous solution at various pH levels. Inductively coupled plasma mass spectrometry (ICP-MS), X-ray diffraction (XRD), field emission electron microscope (FESEM), transmission electron microscopy (TEM), and X-ray photoelectron microscopy (XPS) were employed to determine the removal efficiency and to characterize the deposition of silver onto the surface of β-MnO₂ particles. The optimum pH for the removal of Ag(I) ions was at pH 4 with 99% removal efficiency under 1 h of visible light irradiation. This phenomenon can be attributed to the electrostatic attraction between β-MnO₂ particles and Ag(I) ions as well as the suppression of electron–hole recombination in the presence of H+ ions.     

CoO/SnO2@NC/S复合材料的制备及其应用于高稳定性锂硫电池正极材料

To improve the sulfur loading capacity of lithium-sulfur batteries (Li–S batteries) cathode and avoid the inevitable “shuttle effect”, hollow N doped carbon coated CoO/SnO₂ (CoO/SnO₂@NC) composite has been designed and prepared by a hydrothermal-calcination method. The specific surface area of CoO/SnO₂@NC composite is 85.464 m2·g–1, and the pore volume is 0.1189 cm3·g–1. The hollow core-shell structure as a carrier has a sulfur loading amount of 66.10%. The initial specific capacity of the assembled Li–S batteries is 395.7 mAh·g–1 at 0.2 C, which maintains 302.7 mAh·g–1 after 400 cycles. When the rate increases to 2.5 C, the specific capacity still has 221.2 mAh·g–1. The excellent lithium storage performance is attributed to the core-shell structure with high specific surface area and porosity. This structure effectively increases the sulfur loading, enhances the chemical adsorption of lithium polysulfides, and reduces direct contact between CoO/SnO₂ and the electrolyte.     

TiB2和Al3Ti对近共晶Al?12.6Si合金组织、力学性能和断裂行为的影响

A near eutectic Al?12.6Si alloy was developed with 0.0wt%, 2.0wt%, 4.0wt%, and 6.0wt% Al?5Ti?1B master alloy. The microstructural morphology, hardness, tensile strength, elongation, and fracture behaviour of the alloys were studied. The unmodified Al?12.6Si alloy has an irregular needle and plate-like eutectic silicon (E_Si) and coarse polygonal primary silicon (P_Si) particles in the matrix-like α-Al phase. The P_Si, E_Si, and α-Al morphology and volume fraction were changed due to the addition of the Al?5Ti?1B master alloy. The hardness, UTS, and elongation improved due to the microstructural modification. Nano-sized in-situ Al₃Ti particles and ex-situ TiB₂ particles caused the microstructural modification. The fracture images of the developed alloys exhibit a ductile and brittle mode of fracture at the same time. The Al?5Ti?1B modified alloys have a more ductile mode of fracture and more dimples compared to the unmodified alloy.     

构建TiO2柱状多层石墨烯纳米复合材料作为降解环丙沙星的高效光催化剂

We successfully constructed TiO₂-pillared multilayer graphene nanocomposites (T-MLGs) via a facile method as follows: dodecanediamine pre-pillaring, ion exchange (Ti4+ pillaring), and interlayer in-situ formation of TiO₂ by hydrothermal method. TiO₂ nanoparticles were distributed uniformly on the graphene interlayer. The special structure combined the advantages of graphene and TiO₂ nanoparticles. As a result, T-MLGs with 64.3wt% TiO₂ showed the optimum photodegradation rate and adsorption capabilities toward ciprofloxacin. The photodegradation rate of T-MLGs with 64.3wt% TiO₂ was 78% under light-emitting diode light irradiation for 150 min. Meanwhile, the pseudo-first-order rate constant of T-MLGs with 64.3wt% TiO₂ was 3.89 times than that of pristine TiO₂. The composites also exhibited high stability and reusability after five consecutive photocatalytic tests. This work provides a facile method to synthesize semiconductor-pillared graphene nanocomposites by replacing TiO₂ nanoparticles with other nanoparticles and a feasible means for sustainable utilization of photocatalysts in wastewater control.     

硫酸溶液中IrO2–ZrO2二元氧化物涂层的电化学行为及耐蚀性

In this study, we prepared Ti/IrO₂–ZrO₂ electrodes with different ZrO₂ contents using zirconium-n-butoxide (C₁₆H₃₆O₄Zr) and chloroiridic acid (H₂IrCl₆) via a sol–gel route. To explore the effect of ZrO₂ content on the surface properties and electrochemical behavior of electrodes, we performed physical characterizations and electrochemical measurements. The obtained results revealed that the binary oxide coating was composed of rutile IrO₂, amorphous ZrO₂, and an IrO₂–ZrO₂ solid solution. The IrO₂–ZrO₂ binary oxide coatings exhibited cracked structures with flat regions. A slight incorporation of ZrO₂ promoted the crystallization of the active component IrO₂. However, the crystallization of IrO₂ was hindered when the added ZrO₂ content was greater than 30at%. The appropriate incorporation of ZrO₂ enhanced the electrocatalytic performance of the pure IrO₂ coating. The Ti/70at%IrO₂–30at%ZrO₂ electrode, with its large active surface area, improved electrocatalytic activity, long service lifetime, and especially, lower cost, is the most effective for promoting oxygen evolution in sulfuric acid solution.     

Pt/CeO_2-ZrO_2催化剂低温催化氧化低浓度正己烷废气

采用浸渍法制备了堇青石蜂窝陶瓷负载Pt/CeO2-ZrO2催化剂,测定了其低温催化氧化活性。结果表明,Pt/CeO2-ZrO2催化剂具有良好的催化活性,Pt负载量大的催化剂活性越好,6%Pt/CeO2-ZrO2催化剂的T50为240℃、T90为272℃,空速为20000h-1,对正己烷净化转化率可达100%,适合正己烷工业废气净化处理。     

Pt/CeO_2-ZrO_2/Al_2O_3/金属载体催化燃烧低浓度甲烷

采用浸渍法制备了Pt/CeO2-ZrO2/Al2O3/金属载体催化剂,测定了其对低浓度甲烷催化燃烧活性。结果表明,Pt/CeO2-ZrO2/Al2O3/金属载体催化剂具有良好的催化活性,Pt负载量大的催化剂活性越好,7%Pt/[CeO2-ZrO2/Al2O3]催化剂的T50为359℃、T90为442℃,空速为15000h-1,1%甲烷转化率可达92%。     

CeO2对甲醇水蒸汽重整反应催化剂的影响

研究了Cu/Zn/Ce/Al催化剂上甲醇水蒸汽重整反应，采用X射线衍射分析和程序升温 试验等技术对催化剂的物相结构和还原特性进行了探讨。结果表明：添加CeO2增加CuO的分散性，提高催化剂的稳定性。     

甲醇裂解的创新实验

为了全面掌握流动法—甲醇裂解实验中催化剂的活性,采用浸渍法制备了Pd/CeO2-ZrO2(Pd/CZ)和Pd-Co/CeO2-ZrO2(Pd-Co/CZ)催化剂。运用X射线衍射、N2吸附-脱附、储氧量测定、CO化学吸附、H2程序升温还原(H2-TPR)和X射线光电子能谱对催化剂进行了表征,考察了其催化甲醇裂解反应活性。结果表明,Co的添加不仅提高了催化剂的储氧性能,而且大大提高了催化剂活性组分的分散程度,同时,使得金属和载体间相互作用增强,增加了Pd周围的电子密度,使Pd保持在部分氧化状态Pdδ+(0δ2),进而提高了甲醇催化裂解反应的活性,280℃时甲醇能达到完全裂解,实验效果得到明显改善。     

Pt/CeO2-CNTs和Pt/CNTs在H2SO4和NaOH中乙醇电氧化活性及循环稳定性研究

为考察pH和CeO2对Pt催化剂乙醇电氧化活性的影响,用循环伏安法比较了Pt/CNTs及Pt/CeO2-CNTs在NaOH和H2SO4介质中的电化学行为,表明催化剂在NaOH介质中活性高于在H2SO4中活性,Pt/CeO2-CNTs活性高于Pt/CNTs活性.因Pt催化剂上乙醇电氧化反应的tafel斜率接近,故活性不同可归于影响交换电流密度的OHad浓度的差别.NaOH中Pt表面OHad吸附起始电位和乙醇电氧化起始电位分别低于H2SO4中起始电位,表明OHad决定着Pt催化剂的乙醇电氧化活性.加速耐久性实验表明,CeO2可改善Pt/CNTs的循环稳定性,Pt/CeO2-CNTs和Pt/CNTs在H2SO4中稳定性优于在NaOH中稳定性.     

铜基和钯基催化剂对甲醇加热裂解规律的影响

采用电加热装置加热甲醇,在 Cu/ZnO/Al2O3（铜基）和纯金属 Pd（钯基）两种催化剂作用下发生裂解反应,通过气相色谱仪对甲醇裂解产物进行分析研究．测量发现,甲醇经过加热催化后其气体的主要成分是 H2、CO、CH4、水蒸气和甲醇蒸汽．对其研究表明：H2体积分数峰值出现在铜基催化剂的高环境温度区域,而钯基催化剂明显有两个温度区域,分别是300,℃和500,℃的温度区域;CO 和 CH4的体积分数在所有的测试点都比较低,均小于3.0%;水蒸气体积分数在铜基催化剂下当环境温度250,℃时最大,最大值接近38%;而钯基催化剂下峰值出现在350,℃,接近17%;甲醇裂解率峰值出现在铜基催化剂的高环境温度区域,在钯基催化剂下则有两个温度区域,分别是300,℃和500,℃;催化前入口温度和催化后出口温度都随甲醇流量的增加而降低．     

电沉积法制备PtRuNi、PtRuMo催化剂及甲醇电氧化性能研究

采用恒电位法在玻碳电极上沉积PtRu、PtRuN i和PtRuMo催化剂,研究了催化剂在硫酸溶液中对甲醇的电氧化性能;采用EDS-SEM观察催化剂的形态和测试催化剂的整体组成.研究结果表明,三种催化剂的组成(原子比)分别为Pt/Ru/Mo=3/1/1,Pt/Ru/N i=5/1/0.13,Pt/Ru=3/1,沉积的粒子为球形,粒径在100~600 nm.三种催化剂对甲醇的电氧化活性依次为PtRuMo>PtRuN i>PtRu.     

预沉淀法制备直接甲醇燃料电池的Pt-Fe/C阴极催化剂

用预沉淀法制备了炭载Pt—Fe（Pt—Fe／C）和炭载Pt（Pt／C）催化剂．发现Pt—Fe／C催化剂对氧还原的电催化活性比Pt／C催化剂高，但对甲醇氧化的电催化活性比Pt／C催化剂差．即使在电解液中有甲醇存在时，Pt—Fe／C催化剂对氧还原的电催化活性仍比Pt／C催化剂高．所以，Pt—Fe／C催化剂适合于用作直接甲醇燃料电池（DMFC）中的阴极催化剂．     

Cu/Mo/CeO_2-ZrO_2催化剂的制备及其三效催化性能

以不同沉淀剂制备的CeO2-ZrO2复合氧化物为载体,采用等体积浸渍法制备了Cu/Mo/CeO2-ZrO2催化剂.研究结果表明,当Ce︰Zr的摩尔比为0.65︰0.35,Mo添加量为6%,Cu负载量为5%时,制得的Cu/Mo/CeO2-ZrO2对CO、C3H6和NO的转化具有更好的催化活性,在该催化剂上,CO、C3H6和NO的T50分别为103℃、248℃和244℃,T90分别为189℃、450℃和321℃.Mo的添加能够使催化剂形成稳定的立方晶相固溶体结构,并且使其颗粒更加细化,从而有利于Cu物种高度分散在催化剂表面,提高了催化剂的性能.     

Hydrogen generation from decomposition of hydrous hydrazine over Ni-Ir/CeO2 catalyst

The synthesis of highly active and selective catalysts is the central issue in the development of hydrous hydrazine(N_2H_4·H_2O) as a viable hydrogen carrier. Herein, we report the synthesis of bimetallic Ni-Ir nanocatalyts supported on CeO_2 using a one-pot coprecipitation method. A combination of XRD, HRTEM and XPS analyses indicate that the Ni-Ir/CeO_2 catalyst is composed of tiny Ni-Ir alloy nanoparticles with an average size of around 4 nm and crystalline CeO_2 matrix. The Ni-Ir/CeO_2 catalyst exhibits high catalytic activity and excellent selectivity towards hydrogen generation from N_2H_4·H_2O at mild temperatures. Furthermore, in contrast to previously reported Ni-Pt catalysts, the Ni-Ir/CeO_2 catalyst shows an alleviated requirement on alkali promoter to achieve its optimal catalytic performance.