甲烷二氧化碳重整用Ni/AC催化剂的阈值效应研究

为研究活性炭负载Ni(Ni/AC)基催化剂在甲烷二氧化碳重整反应中的阈值效应,采用N2吸附(BET)和X射线衍射(XRD)测试技术对活性炭负载Ni(Ni/AC)基催化剂进行分析,分别探讨了浸渍溶剂和负载量对催化剂表面结构、Ni分散状态和分散阈值的影响。结果表明,采用丙酮作为溶剂制备的催化剂比纯水在活性炭载体表面更有利镍的分散,提高了活性组分有效面积,并具有更高的分散阈值。对比密置单层排列模型计算值认为Ni在AC表面呈非密置单层或亚单层分散。Ni/AC催化重整甲烷二氧化碳实验结果显示,丙酮作为浸渍溶剂比纯水制备的催化剂表现出更好的催化活性,负载型Ni/AC催化剂在甲烷二氧化碳重整反应中存在显著的阈值效应。     

Ni/γ-Al_2O_3对二氧化碳加氢甲烷化的催化活性研究

比较了不同方法制备的Ni/γ-Al2O3催化剂的催化活性和比表面积,探究了Ni的最佳负载量、Ce对催化剂的改性以及温度、压力、氢碳比对催化剂活性的影响,并进行了XRD、BET分析测试。结果表明Ni的最佳负载量为10%,且γ-Al2O3表面单层Ni分布的最大容量应该在8%~10%之间;2.5%Ce助剂能提高二氧化碳转化率和甲烷选择;而最佳反应条件为:400℃、0.1 MPa、氢碳比为4。     

Ni2P/TiO2上噻吩加氢脱硫性能研究

在10%H2/N2流动气氛下,用程序升温还原方法由相应的磷酸盐合成了二氧化钛负载磷化镍(Ni2P/TiO2)催化剂,用X射线衍射(XRD)、低温N2吸附(BET)等技术对催化剂的结构和性质进行了表征,在高压连续流动固定床反应装置上以噻吩为模型化合物,考察该催化剂的制备条件对其加氢脱硫性能的影响.结果表明,由Ni/P摩尔比为1/2和1/3的前驱体制备的催化剂表面仅出现Ni2P物相;由Ni/P摩尔比为1/1的前驱体制备的催化剂表面出现的主要物相为Ni2P,同时还存在少量Ni12P5相.催化剂的比表面积随前驱体中Ni和P含量的增加而减小.在温度370℃,压力3.0 MPa,VHSV为2 h-1,氢油比(v/v)为450的反应条件下,由Ni负载量为15%(wt)、Ni/P摩尔比为1/2的前驱体所制得Ni2P/TiO2催化剂对含硫0.1%(wt)油具有接近100%的脱硫转化率,并有良好的稳定性.加氢脱硫反应工艺条件研究结果表明:压力、液时进料体积空速以及氢油比对Ni2P/TiO2催化剂对噻吩加氢脱硫性能影响在较宽的范围内变化不大.反应温度对该催化剂上的噻吩加氢脱硫反应的影响较大,当反应温度高于300℃,催化剂对噻吩加氢脱硫性能达到接近100%的脱硫率.     

载镍活性炭脱硫及其再生影响因素研究

钢铁企业烧结烟气温度较低且具有多污染物排放特点.活性炭是一种具有丰富孔隙结构和巨大比表面积的碳质吸附材料,且负载镍活性炭有较好的低温脱硫性能.为深入探究负载镍活性炭用于钢铁企业烧结烟气低温脱硫的可行性,本文以椰壳活性炭为研究对象,采用硝酸镍浸渍法制备载镍活性炭,并开展了催化剂脱硫和再生影响因素研究.研究表明:Ni负载量为1％时,催化剂具有最佳的脱硫能力;60℃为1 Ni/AC催化剂的最佳脱硫反应温度;入口SO2质量分数为0.1％～0.3％和低空速有利于脱硫反应的进行.提升再生温度可提高1 Ni/AC再生率,但再生温度超过400℃后再生率基本维持恒定;初始再生速率与再生温度成正比;载气流量对再生率基本没有影响,只影响再生速度;再生次数的增加使1 Ni/AC硫容随之降低且质量损耗率逐渐增大.研究成果可为活性炭治理钢铁企业烧结烟气多污染物及失活活性炭再生提供借鉴.     

制备条件对Ni_2P/TiO_2-Al_2O_3催化剂的HDN性能影响

采用原位还原技术制备出Ni2P/TiO2-Al2O3催化剂,以喹啉为模型化合物对催化剂的加氢脱氮性能进行评价。主要考察复合载体中不同钛铝配比、不同Ni/P摩尔比对催化剂活性的影响及确定活性组分Ni2P负载量,确定该加氢脱氮催化剂最佳制备方法为:当n(Ti)/n(Al)=1/4,Ni2P负载量25%(wt)。在压力为3 MPa,体积空速为3 h-1,氢油体积比为500,反应温度为360℃的条件下,催化剂的加氢脱氮活性最高,可达98%。     

Ni_2P催化剂的合成及其电解水制氢性能研究

通过次磷酸盐还原法制备磷化镍催化剂,考察了不同Ni/P摩尔比、烧结温度制备的磷化镍催化剂对电催化分解水产氢性能的影响。结果表明,磷化镍产物的结构组成以Ni_2P为主,不同Ni/P摩尔比(1∶2～1∶6)对Ni_2P电催化分解水产氢的性能有重要影响,呈现先增后减的趋势,当Ni/P摩尔比为1∶4时Ni_2P电解水产氢活性最高;此外,在250～550℃范围内,随着烧结温度的升高,Ni_2P电解水产氢的性能呈递减的趋势。     

负载Ni催化剂表面Ni的形态及其甲烷化活性研究

采用浸渍法制备了具有不同Ni负载量的NiO/γ-Al2O3催化剂,经过不同温度下的焙烧处理后得到一系列共9个催化剂样品。借助X射线光电子能谱分析比较Ni负载量和焙烧处理温度对Ni在催化剂载体表面存在的形态。结果表明,对于Ni负载量为10%的样品,Ni离子会在催化剂表面以八面体配位的镍和表面尖晶石NiAl2O4的形态存在,随着焙烧温度的提高,以表面尖晶石NiAl2O4形式存在的Ni的比例也增加;当Ni负载量达到20%以上,以NiO形态存在的Ni会更多的出现在催化剂表面,而提高焙烧温度不利于NiO的存在。CO甲烷化微反评价的结果显示,表面富集NiO的催化剂具有更好的甲烷化催化活性。     

Ni-Mo合金电极的制备条件对其析氢性能的影响

采用电沉积技术制备了N i-M o合金电极,研究了电流密度、pH、温度对电极析氢催化活性的影响,得出了较适宜的工艺配方,该配方下制备的合金结构介于晶态和非晶态之间,具有较好的析氢催化活性。在28%的KOH溶液中,析氢电流密度为100 mA/cm2时,析氢电位比N i电极降低近300 mV。     

Ni/AC催化α-羟基丙酮加氢制1,2-丙二醇反应研究

制备了一系列Ni/AC催化剂,以α-羟基丙酮催化加氢制备1,2-丙二醇为目标反应,系统考察了Ni/AC催化剂的制备条件和反应工艺条件,结果表明催化剂的Ni负载量为15%,在550℃下煅烧4 h、H2气氛400℃还原4 h获得的催化剂为高分散的金属Ni物种,所得催化剂在质量空速1.4 h-1、反应温度280℃、α-羟基丙酮质量分数为50%的最优条件下,转化率达到了70.6%,1,2-丙二醇选择性为96.2%。     

负载TiO2城市污泥改性物光催化剂的制备

用城市污水处理厂的剩余污泥作原料,炭化制备活性炭吸附剂。以钛酸丁酯和无水乙醇为原料,乙酸为水解抑制剂,采用溶胶-凝胶法制备纳米TiO2粉体,利用浸渍-烧结法将其负载于制备的污泥活性炭上,获得TiO2/AC光催化剂。以重金属离子Hg2+为目标污染物进行光催化去除实验,考察了抑制剂用量、TiO2的负载量、煅烧温度等对TiO2/AC催化性能的影响。结果表明,当CH3COOH∶Ti(OBu)4=0.8～1.0时,对Hg2+的催化去除效果较好;TiO2负载量为33.3%时,TiO2/AC光催化剂具有良好的吸附性能和更高的催化活性;煅烧温度直接影响晶体的结构,550℃煅烧时生成的混合晶体具有较高的催化性能。在最佳条件下制备的TiO2/AC光催化剂对水溶液中20 mg/L的Hg2+的光催化去除率可达到88.5%。     

以KMnO4改性炭黑为载体的Pd-Ni催化剂的制备和性能

以不同浓度的KMnO4溶液预处理的炭黑为载体，通过沉淀共还原法合成了3种Pd1Ni1/ACx (x=3,5,7)催化剂，并将3种催化剂与商业Pd/C催化剂进行了性能对比。用XPS、ICP、XRD和TEM对催化剂了进行表征。结果表明：Pd1Ni1/AC5的Pd负载量（质量分数，下同）最大（3.66%），Pd晶粒的平均粒径最小（4.71 nm），且均匀地分布在KMnO4氧化处理后的碳载体上，活性位点较多；XRD显示，3种Pd1Ni1/ACx催化剂中的Ni均以无定形存在。在电化学性能测试中，3种催化剂均表现出比商业Pd/C更好的电化学稳定性和存活率；其中，Pd1Ni1/AC5电化学活性表面积达62.21 m2/gPd，且乙醇催化活性为1797.85 A/gPd。     

Electro-catalytic oxidation of CO on Pt catalyst supported on carbon nanotubes pretreated with oxidative acids

Characteristics of nanosized Pt electro-catalyst deposited on carbon nanotubes (CNTs) were studied with CO-stripping voltammogram and chronoamperometry measurements. The CNTs were pretreated by oxidation in HNO₃, mixed HNO₃ + H₂SO₄ and H₂SO₄ + K₂Cr₂O₇ solution, respectively, to enable surface modification. Well-homogenized Pt particles (average size: ≈3 nm) were loaded onto the pretreated CNT samples by a modified colloidal method. TEM, BET, FTIR and XRD techniques were used to characterize the physicochemical properties of the pretreated CNT samples. In the electro-oxidation of CO, all the Pt/CNT samples showed lower on-set as well as peak potentials than the conventional Pt/XC-72 electro-catalyst, indicating that the Pt/CNT samples were more resistant to CO poisoning and could be superior anode electro-catalyst for the proton exchange membrane fuel cells (PEMFCs). Moreover, we found that the pretreatment of CNTs in mixed HNO₃ + H₂SO₄ solution was very beneficial for the performance enhancement of Pt/CNT electro-catalyst; the catalyst obtained as such gave the lowest peak potential and the highest catalytic activity for the electro-oxidation of CO. Larger amount of oxygen-containing functional groups, higher percentage of mesopores, and higher graphitic crystallinity of the pretreated CNTs were considered crucial for the performance enhancement, e.g., by strengthening the interaction between Pt nanoparticles and the CNT support and enhancing the mass diffusion in the electro-chemical reaction.     

Catalytic behavior of carbon supported Ni-B, Co-B and Co-Ni-B in hydrogen generation by hydrolysis of KBH4

Activated carbon (AC) supported Ni-B, Co-B, and Co-Ni-B catalysts with different Co/Ni mass ratios were synthesized by impregnation of commercial activated carbon with the solution of cobalt and/or nickel salt, and then reduction of metal salts with sodium borohydride at room temperature. Structural properties and morphology of the catalysts were studied using inductively coupled plasma (ICP), XRD and SEM techniques. The B content of the catalyst is less than that required for stoichiometric alloy formation, which indicates the simultaneous presence of the Co and/or Ni metal along with Co-B and/or Ni-B alloy on the surface of activated carbon. The catalytic activity of the catalysts has been tested by measuring the hydrogen generation rate during the hydrolysis of potassium borohydride in basic medium. The results show that Co-B/AC exhibits the highest activity among Ni-B/AC, Co-B/AC and Co-Ni-B/AC catalysts investigated. For supported bimetallic boride catalysts, the catalytic activity increases with Co/Ni mass ratio. The effects of reaction parameters, such as KBH₄ concentration, NaOH concentration, and reaction temperature, on the reaction were also surveyed.     

Redox poly[Ni(saldMp)] modified activated carbon electrode in electrochemical supercapacitors

The complex (2,2-dimethyl-1,3-propanediaminebis(salicylideneaminato))-nickel(II), [Ni(saldMp)], was oxidatively electropolymerized on activated carbon (AC) electrode in acetonitrile solution. The poly[Ni(saldMp)] presented an incomplete coated film on the surface of carbon particles of AC electrode by field emission scanning electron microscopy. The electrochemical behaviors of poly[Ni(saldMp)] modified activated carbon (PAC) electrode were evaluated in different potential ranges by cyclic voltammetry. Counterions and solvent swelling mainly occurred up to 0.6 V for PAC electrode by the comparison of D^1/2C values calculated from chronoamperometry experiments. Both the Ohmic resistance and Faraday resistance of PAC electrode gradually approached to those of AC electrode when its potential was ranging from 1.2 V to 0.0 V. Galvanostatic charge/discharge experiments indicated that both the specific capacitance and energy density were effectively improved by the reversible redox reaction of poly[Ni(saldMp)] film under the high current density up to 10 mA cm⁻² for AC electrode. The specific capacitance of PAC electrode decreased during the first 50 cycles but thereafter it remained constant for the next 200 cycles. This study showed the redox polymer may be an attractive material in supercapacitors.     

Promoting effect of CeO2 addition to Ni/AC catalyst for vapor phase carbonylation of ethanol to propionic acid

Ni/AC catalysts promoted with or without CeO₂ for vapor phase carbonylation of ethanol to propionic acid were tested and investigated by CO chemisorption, XRD and H₂-TPR techniques. The catalytic test results showed that the proper amount of CeO₂ addition could remarkably enhance the activity and stability of Ni/AC catalyst. The characterization results indicated that CeO₂ added can improve the dispersion and metal area of Ni on the catalyst, suppress the sintering of Ni crystallite and benefit the reduction of Ni, which are closely related to high performance of the Ni/AC catalyst promoted with CeO₂.     

Controlling the yield and structure of carbon nanofibers grown on a nickel/activated carbon catalyst

Carbon nanofibers (CNFs) were grown via the chemical vapor deposition of C₂H₄ on an activated carbon (AC)-supported Ni catalyst. The texture of the CNF/AC composites can be tuned by varying the growth temperature and by treatment in reducing atmosphere prior to C₂H₄/H₂ exposure. The Ni-catalyzed gasification of the AC support increases the microporosity of the composite and shown to be dominant throughout the composite synthesis especially during reduction, subsequent treatment in reducing atmosphere, and CNF growth at low temperatures. N₂ isotherm and scanning electron microscope were used to characterize the texture and morphology of the composites. Subsequent treatment in reducing atmosphere were shown to increase the Ni catalyst activity to grow CNFs. High resolution transmission electron microscope however did not reveal any microstructural difference for Ni catalyst with and without the subsequent reduction treatment. We propose in this paper that the carbon dissolutions during treatment of the catalyst might have an implication on the CNF growth.     

PVA基碱性聚合物电解质Ni(OH)2/AC超级电容器的电化学性能

Polyvinyl alcohol(PVA)-sodium polyacrylate(PAAS)-KOH-H₂O alkaline polymer electrolyte film with high ionic conductivity was prepared by a solution-casting method.Polymer Ni(OH)₂/activated carbon(AC) hybrid supercapacitors with different electrode active material mass ratios(positive to negative) were fabricated using this alkaline polymer electrolyte,nickel hydroxide positive electrodes,and AC negative electrodes.Galvanostatic charge/discharge and electrochemical impedance spectroscopy(EIS) methods were used to study the electrochemical performance of the capacitors,such as charge/discharge specific capacitance,rate charge/discharge ability,and charge/discharge cyclic stability.Experimental results showed that with the decreasing of active material mass ratio m(Ni(OH)₂)/m(AC),the charge/discharge specific capacitance increases,but the rate charge/discharge ability and the charge/discharge cyclic stability decrease.     

甲醇羰基化双组分催化剂表征研究

采用浸渍法制备了Ni/AC单组分催化剂和Ni-Mo/AC双组分催化剂,用固定床催化反应器评价了催化剂性能,实验证明Ni-Mo/AC可使甲醇的转化率达到93.86%,羰化产物收率达到62.71%。通过XRD、XPS、BET等手段对催化剂进行了表征。结果表明,少量Mo的加入,改变了Ni的表面状态以及Ni与活性炭之间的相互作用,Mo与Ni相互作用形成催化活性中心。Mo主要作为结构型助剂,可使NiO易于还原,增加了羰化活性中心数量,提高了催化剂的活性。     

钯炭催化剂载体对莫西沙星侧链中间体合成的影响

改进了用于莫西沙星侧链中间体合成的钯炭催化剂制备工艺,主要讨论载体材质、粒度及处理方式对催化剂性能的影响。结果表明,选择椰壳炭为载体,粒度(300~400)目,用氢氧化钠处理的载体制备的催化剂与现售催化剂相比,选择性提高2个百分点,重复使用性能提高33%。     

Ni(OH)2/活性炭复合材料在超级电容器中的应用

用化学沉淀法在活性炭(AC)表面和微孔内掺杂不同量的氢氧化镍,制备了氢氧化镍-活性炭[Ni(OH)2-AC]复合材料. 用X射线衍射(XRD)和氮气吸附等温线等对活性炭和复合材料进行表征,结果表明,所制材料为b-Ni(OH)2-AC复合材料. 对不同掺杂量的b-Ni(OH)2-AC复合材料的电化学性能进行了研究,循环伏安、恒流充放电实验表明,少量氢氧化镍掺入活性炭表面和微孔中,所得材料的比电容较活性炭有所提高,并具有良好的充放电性能;当氢氧化镍的掺入量为6%(w)时,所制备的超级电容器单电极表现出优良的电化学性能. 以活性炭电极作负极,复合材料作正极制成复合型超级电容器,循环性能测试发现,掺入6%(w)氢氧化镍的复合材料制成的Ni(OH)2-AC/AC复合型超级电容器比电容高达330.7 F/g,比活性炭(AC/AC)超级电容器比电容(245.6 F/g)提高了34.6%,且Ni(OH)2-AC/AC复合型超级电容器具有更好的循环充放电性能.