Investigating the performance of a Rh metal catalyst in hydrogen–deuterium exchange reactions in methane for application in low-temperature membrane separators

The development of safe, efficient, and cost effective methods to recover waste components of deuterium–tritium (D–T) plasma reactors, including hydrogen and methane, has attracted much interest in the scientific community. Typically, membrane separators are used for this process, although several problems occur when performing separations at higher temperatures. The application of noble metal catalysts may improve the reaction dynamics and allow the separation process to occur at lower temperatures. In this paper, a series of noble metal catalysts were prepared by a traditional dipping method. Based on an analysis of catalytic performance, the Rh/Al₂O₃ catalyst was determined to be the most suitable for the exchange of hydrogen and deuterium in methane. The catalyst was characterized by X-ray diffraction, X-ray photoelectron spectroscopy, and temperature programmed reduction analyses. The effects of the metal loading and experimental conditions were also investigated.     

MoP with rich species generated via radio frequency thermal plasma for higher alcohols synthesis from syngas

In this paper, the molybdenum phosphide (MoP) catalysts (TPR-MoP and TPR-MoP-Pla) were prepared by the traditional method and the RF (radio frequency) thermal plasma technique respectively and characterized by x-ray diffraction (XRD), x-ray photoelectron spectroscopy (XPS), transmission electron microscope (TEM), hydrogen temperature-programmed desorption (H₂-TPD) and carbon monoxide temperature-programmed desorption (CO-TPD) measurements, and their catalytic performance for HAS was evaluated. The results showed that the total and C₂₊ alcohols selectivity of the catalyst after plasma treatment (TPR-MoP-Pla) were enhanced. The enhanced catalytic performance could be related to more dislocation defects and the synergistic effect between Mo^0–2+ and Mo⁴⁺ valence species in the TPR-MoP-Pla catalyst. In addition, this work suggests that thermal plasma treatment can be used as a new preparation technique for the synthesis of materials with rich species.     

Hydrochlorination of acetylene over the Ru-based catalysts treated by plasma under different atmospheres

Ru-based catalysts modified in different atmospheres by plasma technology were prepared to catalyze the acetylene hydrochlorination reaction. The (Ru/AC)-N₂ (AC = activated carbon) catalyst yielded by the plasma modification of Ru/AC catalyst in N₂ atmosphere exhibits the best catalytic performance with a stable C₂H₂ conversion of 87.2%; a relative increase of 27.1% in C₂H₂ conversion was achieved compared with that of the untreated Ru/AC catalyst. The results of the analysis revealed that the modification produced a mutual effect between the generated function groups on carrier AC and the active components, which can disperse and yield more active species in the fresh catalysts. These are benefits of enhancing the activity of the catalysts. Moreover, the modification can restrain coke formation and inhibit the loss of active species in the reaction, as well as strengthen the adsorption ability of reactants on the catalysts. These are benefits of improving the catalysts’ performance.     

催化化学中的核技术—PASCA

介绍近年来应用ＰＡＳＣＡ技术研究石油加工催化剂方面的进展，其中某些结果已直接用于指导新型指导新型催化剂的开发，并取得了相当的成功。     

光化学分离水溶液中铂族金属元素的研究——Pd(Ⅱ)的光还原

采用光化学法将Na2PdCl4水溶液中的二价钯离子(Pd(Ⅱ))还原至钯单质,通过改变照射光波长、自由基清除剂种类、Cl-浓度、pH值等参数以获得光还原Pd(Ⅱ)的最佳条件。采用紫外-可见吸收光谱(UV-vis)和X射线光电子能谱(XPS)等表征手段分别对上清液和生成的沉淀进行表征。结果表明:使用光化学法能成功地还原出水溶液中的钯离子,提取率可达98.4%;相比之下,采用异丙醇作为自由基清除剂时能更有效地提取溶液中的钯元素。高浓度的Cl-抑制Pd(Ⅱ)的还原;适当提高pH值可以促进Pd(Ⅱ)的还原。此外,还验证了从Na2PdCl4和NdCl3混合溶液中光还原并分离Pd(Ⅱ)的可行性。     

Pt/C对氢同位素交换反应的催化性能研究

采用并流法研究了用不同活性炭担体制备的Pt/C对H2（g）/HDO（v）体系的催化性能,得出Pt/C对氢-水同位素交换反应的活化能为41.3～42.4kJ•mol－1。实验结果表明,采用表面改性活性炭制备的Pt/C对H2（g）/HDO（v）的催化活性比未经改性活性炭制备的Pt/C高出1倍,但两者对水蒸气均为0.77±0.05级反应,其活化能也基本相等,说明活性炭担体表面改性未改变Pt/C对氢-水同位素交换的反应机理。     

电子束辐照制备Pd/TiO2光催化薄膜

用电子束辐照浸泡在浓度分别为1×10-5、1×10-4、1×10-3、1×10-2和1×10-1mol/L的PdCl2溶液中的TiO2薄膜,在TiO2薄膜表面形成Pd纳米颗粒.通过X射线衍射(X-ray diffractometry,XRD)、场发射扫描电镜(Field emission scanning electron microscope,FESEM)、X射线光电子能谱(X-ray photoelectron spectroscopy,XPS)和紫外可见(Ultraviolet visible,UV-Vis)吸收光谱对辐照后的Pd/TiO2薄膜进行表征.分析表明,TiO2薄膜表面上沉积了直径20-50 nm的颗粒,为面心立方结晶的金属Pd;Pd/TiO2薄膜的UV-Vis光谱吸收边向可见光方向发生了偏移.用甲基橙作为光催化降解反应物,研究了Pd/TiO2薄膜分别在紫外光、可见光作用下的光催化降解效率.结果表明,Pd/TiO2薄膜的光催化能力显著地提高,在紫外光、可见光作用下的光催化效率分别提高了2.25倍和3.4倍.     

空气除氚系统中氚氧化催化剂的研究进展

在大型氚设施中空气除氚系统必不可少,通过气-水转换除去气态氚是目前应用最广泛也是最有效的工艺,过程中氧化催化剂至关重要。总结了气态氚的催化氧化研究进展、催化剂的催化性能及影响催化性能的主要因素。贵金属Pt和Pd在室温下对氚的转化效率接近100%,因而被广泛用于氚的催化氧化。通过负载分散载体、添加催化助剂、使用规整结构催化剂、设计新型的催化反应器能够进一步提高催化剂性能。以蜂窝状催化剂为研究热点的规整结构催化剂以其高比表面积和低压力降而显示出良好的催化性能,将它用于氚的催化氧化,是该领域的一个研究方向。氢、氘、氚在氧化过程中的同位素效应会影响除氚效率,需进行深入研究。     

负载型Ru/γ-Al2O3催化剂上甲烷与氘化氢之间的氢氘交换性能

实验研究了以浸渍法制备的负载型Ru/γ-Al2O3催化剂体系上甲烷与氘化氢之间的氢氘交换性能,考察了各反应工艺条件包括反应温度、反应原料气流量、反应原料气中HD/CH4的比等因素对Ru/γ-Al2O3催化剂上甲烷与氘化氢之间的氢氘交换性能的影响,采用程序升温还原（H2-TPR）和X射线粉末衍射（XRD）手段对催化剂进行了检测。实验结果表明,Ru和载体γ-Al2O3发生了强相互作用;在对甲烷与氘化氢间的氢氘交换反应中,Ru/γ-Al2O3催化剂显示出较好的催化活性和稳定性。     

Atmospheric-Pressure DBD Cold Plasma for Preparation of High Active Au/P25 Catalysts for Low-Temperature CO Oxidation

Cold plasma generated by dielectric barrier discharge (DBD) at atmospheric pressure was adopted for preparation of commercial TiO2 Degussa P25 supported Au catalysts (Au/P25-P) with the assistance of the deposition-precipitation procedure.The influences of the plasma reduction time and calcination on the performance of the Au/P25-P catalysts were investigated.CO oxidation was performed to investigate the catalytic activity of thc Au/P25 catalysts.The results show that DBD cold plasma for the fabrication of Au/P25-P catalysts is a fast process,and Au/P25-P (4 min) exhibited the highest CO oxidation activity due to the complete reduction of Au compounds and less consumption of oxygen vacancies.In order to form more oxygen vacancies active species,Au/P25-P was calcined to obtain Au/P25-PC catalysts.Interestingly,Au/P25-PC exhibited the highest activity for CO oxidation among the Au/P25 samples.The results of transmission electron microscopy (TEM) indicated that the smaller size and high distribution of Au nanoparticles are the mean reasons for a high performance of Au/P25-PC.Atmospheric-pressure DBD cold plasma was proved to be of great efficiency in preparing high performance supported Au catalysts.     

氢-水液相交换疏水催化剂制备及活性影响因素研究进展

氢-水液相催化交换反应（LPCE）可用于含氚废水处理、含氚重水提氚、重水升级和重水生产等工艺,疏水催化剂是实现LPCE的关键。本文对疏水催化剂的制备方法及活性影响因素进行了综述,重点介绍了Pt/C/惰性载体类疏水催化剂的研究进展,包括惰性载体、活性金属载体的选择,碳负载Pt基催化剂制备方法,详细介绍了围绕疏水催化剂制备开展的基础研究工作,如LPCE微观反应机理,活性金属微观结构与催化活性的关系等。对疏水催化剂这一领域有待解决的问题及下一步的研究方向进行了探讨。     

Plasma-assisted Co/Zr-metal organic framework catalysis of CO_2 hydrogenation:influence of Co precursors

In this study, Co/Zr-metal organic framework(MOF) precursors were obtained by a roomtemperature liquid-phase precipitation method and the equivalent-volume impregnation method,respectively, using a Zr-MOF as the support, and Co/Zr-MOF-M and Co/Zr-MOF-N catalysts were prepared after calcination in a hydrogen–argon mixture gases(V_(Ar):V_(H_2)= 9: 1) at 350 °C for 2 h. The catalytic activities of the prepared samples for CO_2 methanation under atmosphericpressure cold plasma were studied. The results showed that Co/Zr-MOF-M had a good synergistic effect with cold plasma. At a discharge power of 13.0 W, V_(H_2):V_(CO_2)= 4: 1 and a gas flow rate of 30 ml·min~(-1), the CO_2 conversion was 58.9% and the CH_4 selectivity reached 94.7%,which was higher than for Co/Zr-MOF-N under plasma(CO_2 conversion 24.8%, CH_4 selectivity 9.8%). X-ray diffraction, scanning electron microscopy, transmission electron microscopy, N_2 adsorption and desorption(Brunauer–Emmett–Teller) and x-ray photoelectron spectroscopy analysis results showed that Co/Zr-MOF-M and Co/Zr-MOF-N retained a good Zr-MOF framework structure, and the Co oxide was uniformly dispersed on the surface of the Zr-MOF. Compared with Co/Zr-MOF-N, the Co/Zr-MOF-M catalyst has a larger specific surface area and higher Co~(2+)/Cototaland Co/Zr ratios. Additionally, the Co oxide in Co/ZrMOF-M is distributed on the surface of the Zr-MOF in the form of porous particles, which may be the main reason why the catalytic activity of Co/Zr-MOF-M is higher than that of Co/ZrMOF-N.     

用于氢-水同位素交换的Pt-PTFE类憎水催化剂的研制

研制了以铂为活性成分，聚四氟乙烯（PTFE）为憎水材料，活性炭、二氧化硅等作载体的憎水催化剂。在滴流床上，进行了氢-水气液逆流氢同位素交换反应，讨论了载体、铂含量及PTEF量对催化剂活性的影响。结果表明，以活性炭为载体，聚四氟乙烯与Pt-C粉的质量比在1-2时，Pt-C-PTFE催化剂的活性高；交换反应的总体积传质系数随反应温度和氢气流量的增加而增大。     

103Pd-110Agm合金膜制备工艺研究

以103Pd和110Agm 为示踪剂,采用化学镀法制备了103Pd-110Agm合金膜,并优化了制备条件：对制得的103Pd-110Agm合金膜采用γ井型探测器进行定量分析,扫描电镜进行定性分析。结果显示,优化后的镀膜条件为：镀液组成为PdCl2(含放射性103Pd) 、AgNO3、Na2EDTA、NH3 、N2H4;Pd与Ag的摩尔比为9∶1;活化液PdCl2的浓度范围为0.5～2.0 mmol/L;金属离子总浓度为5～7 mmol/L;NH3浓度为2～4 mol/L;pH为10～12;N2H4浓度为10 mmol/L;Na2EDTA浓度为0.15 mol/L;恒温水浴槽保持温度为60 ℃,旋转搅拌器转速为40～60 r/min,反应时间为60 min。在以上镀膜条件下进行化学镀,可得到具有金属光泽的镀层。用载体预处理后,扫描电镜显示,镀层表面有晶粒生长,镀后清晰可见;定性分析结果表明,合金膜中有Pd、Ag元素存在。     

Fischer-Tropsch Performance of an SiO2-Supported Co-Based Catalyst Prepared by Hydrogen Dielectric-Barrier Discharge Plasma

A silica-supported cobalt catalyst was prepared by hydrogen dielectric-barrier dis- charge （H2-DBD） plasma. Compared to thermal hydrogen reduction, H2-DBD plasma treatment can not only fully decompose the cobalt precursor but also partially reduce the cobalt oxides at lower temperature and with less time. The effect of the discharge atmosphere on the property of the plasma-prepared catalyst and the Fischer-Tropsch synthesis activity was studied. The re- sults indicate that H2-DBD plasma treatment is a promising alternative for preparing Co/SiO2 catalysts from the viewpoint of energy savings and efficiency.     

Applicability of a catalytic reduction method using a palladium–copper catalyst and hydrazine for the denitration of a highly concentrated nitrate salt solution

Denitration of a highly concentrated sodium nitrate (NaNO₃) aqueous solution via a catalytic reduction method using a palladium–copper catalyst supported on carbon powder (Pd–Cu/C) and hydrazine (N₂H₄) was investigated. It was demonstrated that nitrate ion (NO₃ ^?) in a 5 mol L^?1 NaNO₃ solution was completely reduced through an intermediate nitrite ion (NO₂ ^?) to nitrogen compounds such as nitrogen, nitrous oxide, and ammonia. By comparing the reaction rates of NO₃ ^? and NO₂ ^? obtained using catalysts with various Pd–Cu compositions and different reductants (hydrogen (H₂) or N₂H₄), it was determined that the catalyst with a molar ratio of Pd:Cu = 1:0.66 provides the maximum reaction rates for NO₃ ^? and NO₂ ^? using N₂H₄, and that not only the reactions of NO₃ ^? and NO₂ ^? but also that of N₂H₄ were affected by the Pd–Cu composition.     

Hydrogen absorption by Pd-coated ZrNi prepared by using Barrel-Sputtering System

To improve the durability of hydrogen storage materials against surface poisoning by impurity gases, effectiveness of Pd-coating layer prepared by using a Barrel-Sputtering System was examined for ZrNi powder. The effectiveness of Pd-coating was evaluated by activation temperature, at which Pd/ZrNi poisoned by air could be activated to absorb hydrogen. Characterization of Pd-coated ZrNi (denoted as Pd/ZrNi) by scanning electron microscopy, electron probe microanalysis and X-ray diffraction showed that a uniform Pd-coating layer was formed with the barrel-sputtering system. It was found that the poisoned Pd/ZrNi sample could be activated even at 423 K to absorb hydrogen at room temperature. This exhibits remarkable contrast to bare ZrNi, which could be only activated appreciably above 1073 K. It is concluded that the Pd-coating by barrel sputtering is quite effective to avoid the effect of surface poisoning of powdery hydrogen storage materials. However, the activation at excessively high temperature resulted in the loss of high activity to absorb hydrogen. It was concluded that this phenomenon was associated with reactions between Pd and ZrNi to form PdZr and other byproducts.     

Plasma-catalytic degradation of tetracycline hydrochloride over Mn/γ-Al2O3 catalysts in a dielectric barrier discharge reactor

A coaxial dielectric barrier discharge (DBD) reactor was used for plasma-catalytic degradation of tetracycline hydrochloride over a series ofMn/γ-Al₂O₃ catalysts prepared by the incipient wetness impregnation method. The combination of plasma and theMn/γ-Al₂O₃ catalysts significantly enhanced the degradation efficiency of tetracycline hydrochloride compared to the plasma process alone, with the 10%Mn/γ-Al₂O₃ catalyst exhibiting the best tetracycline hydrochloride degradation efficiency. A maximum degradation efficiency of 99.3% can be achieved after 5 min oxidation and a discharge power of 1.3 W, with only 69.7% by a single plasma process. The highest energy yield of the plasma-catalytic process is 91.7 gkWh⁻¹. Probable reaction mechanisms of the plasma-catalytic removal of tetracycline hydrochloride were also proposed.     

反应堆非能动氢气复合器严重事故下消氢性能研究

非能动氢气复合器（PAR）是核电厂主要的消氢措施。在严重事故下,某些裂变反应产生的特殊杂质(如I₂、CsI、CO等)可能对催化剂产生有害的影响,为保证PAR消氢性能的可靠性,中毒机理研究十分必要。本文根据相关试验研究结果,从铂、钯金属原子分布结构、催化反应性面积两个方面对催化剂中毒效应进行机理分析,研究得出催化剂中金属原子的分布结构、进入PAR的实际毒物浓度等均是影响催化剂中毒效应的关键因素。