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1.
O. V. Dolgikh Yu. G. Kravtsova N. V. Sotskaya 《Russian Journal of Electrochemistry》2010,46(8):918-924
The effect of composition and structure of electrodeposited nickel-phosphorus coatings on their catalytic properties in the
hydrogen evolution reaction is studied. It is found that an increase in the content of phosphorus in the alloy from 0.1 to
12.6 wt % leads to an increase in the hydrogen evolution rate. The coatings, which were deposited under the galvanostatic
conditions, exhibit higher activity than those plated under the potentiodynamic conditions. It is shown that the nature of
acceleration of hydrogen evolution rate on the alloys depends on the alloy composition: only Ni-P alloys containing up to
6.5 wt % phosphorus possess true catalytic activity, whereas the coatings enriched in phosphorus promote the hydrogen evolution
due to significant development of their surface area. 相似文献
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Chang Yuan HU Feng Yi LI Rong Bin ZHANG Li HUA 《中国化学快报》2006,17(1):109-112
Carbon nanotubes (CNTs) are severely bundled and essentially insoluble in solvent. These properties are generally considered as a significant barrier toward the practical uses of CNTs. Therefore, the functionalization and solubilization of CNTs have recei… 相似文献
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Electrocatalytic behavior of electroless Ni-P alloys for the oxygen evolution reaction 总被引:2,自引:0,他引:2
The structural and morphological characteristics of electroless nickel phosphorous films (P content from 4.0 to 13.8 at %)
are described. Different treatments such as heat (400°C, 1 h) or electrochemical (anodizing at 0.5 V vs. SCE followed by multi-cycle
polarization) are employed and their effect on the alloys properties is analyzed using x-ray diffraction and atomic force
microscopy. Information on the performance of the as-deposited and treated electroless Ni-P coatings as anodes for oxygen
evolution reaction, in alkaline media, is taken from the steady state polarization curves and the correspondent Tafel slopes.
The data shows the importance of the deposit crystalline nature and of the electrochemical treatment on the formation of β-Ni(OH)2 and subsequently β-Ni(OOH), crucial for obtaining Ni-P films with good electrocatalytic properties.
Published in Russian in Elektrokhimiya, 2006, Vol. 42, No. 12, pp. 1427–1434.
Based on the report delivered at the 8th International Frumkin Symposium “Kinetics of the Electrode Processes.” October 18–22,
2005, Moscow.
The text was submitted by the authors in English. 相似文献
5.
V. M. Krutskikh A. B. Drovosekov Yu. M. Polukarov B. F. Lyakhov A. D. Aliev V. M. Martynenko Yu. M. Shul’ga 《Russian Journal of Electrochemistry》2012,48(5):556-563
The gaseous products of the oxidation of hydride hydrogen of the dimethylamine borane (DMAB) (CH3)2NH · BH3 reducer used for depositing Ni-Re-B coatings and hydrolysis of DMAB on them were studied by mass spectrometry of the isotope composition of the gas. The oxidation level of hydride hydrogen of the DMAB reducer was found to depend on the catalytic activity of the Ni-Re-B alloy, on which heterogeneous hydrolysis takes place. For Ni-Re-B alloys with low rhenium concentrations (0?C13 at %), the heterogeneous hydrolysis of DMAB proceeds with hydride hydrogen oxidation to the atomic state, as it does in the deposition of the Ni-B alloy. In contrast, at high rhenium concentrations (40?C46 at %), the oxidation proceeds to the proton H+, leading to an antibatic dependence of the hydrolysis and alloy reduction rates. An analysis of the partial rates of the process and isotope composition of the evolved gas revealed two different mechanisms of the chemical-catalytic reduction of Ni-Re-B alloys at concentrations of potassium perrhenate of 0?C4 and 4?C16 mM in solution. 相似文献
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以膨胀石墨担载壳聚糖,采用金属诱导化学镀法制备了负载型Ni—B非晶态合金催化剂.通过X射线衍射、电感耦合等离子体发射光谱、扫描电子显微镜、透射电子显微镜和选区电子衍射等技术研究了壳聚糖对Ni-B催化剂非晶性质、组成、形貌、粒径及分散度的影响.以环丁烯砜加氢制环丁砜和对氯硝基苯加氢制对氯苯胺为探针反应,考察了壳聚糖对负载型Ni-B非晶态合金催化剂催化性质的影响,讨论了壳聚糖用量及水溶性壳聚糖的相对分子质量对催化剂性质的影响.结果表明,壳聚糖介质的引入能够提高活性组分的分散度,减小活性组分的粒径,从而明显提高了催化剂的催化加氢活性.当壳聚糖在载体表面形成单层分散时催化剂活性最高.分子质量相对较低的水溶性壳聚糖有利于生成粒径小、分散性好和催化活性高的Ni—B非晶态合金催化剂. 相似文献
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以壳聚糖为介质的Ni-B非晶态合金/膨胀石墨的制备及其催化加氢性能 总被引:1,自引:0,他引:1
以膨胀石墨担载壳聚糖,采用金属诱导化学镀法制备了负载型Ni-B非晶态合金催化剂.通过X射线衍射、电感耦合等离子体发射光谱、扫描电子显微镜、透射电子显微镜和选区电子衍射等技术研究了壳聚糖对Ni-B催化剂非晶性质、组成、形貌、粒径及分散度的影响.以环丁烯砜加氢制环丁砜和对氯硝基苯加氢制对氯苯胺为探针反应,考察了壳聚糖对负载型Ni-B非晶态合金催化剂催化性质的影响,讨论了壳聚糖用量及水溶性壳聚糖的相对分子质量对催化剂性质的影响.结果表明,壳聚糖介质的引入能够提高活性组分的分散度,减小活性组分的粒径,从而明显提高了催化剂的催化加氢活性.当壳聚糖在载体表面形成单层分散时催化剂活性最高.分子质量相对较低的水溶性壳聚糖有利于生成粒径小、分散性好和催化活性高的Ni-B非晶态合金催化剂. 相似文献
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Evaluation of the corrosion resistance of electroless Ni-P and Ni-P composite coatings by electrochemical impedance spectroscopy 总被引:4,自引:0,他引:4
J. Balaraju T. Sankara Narayanan S. Seshadri 《Journal of Solid State Electrochemistry》2001,5(5):334-338
Electroless Ni-P composite coatings have gained a good deal of popularity and acceptance in recent years as they provide
considerable improvement of desirable qualities such as hardness, wear, abrasion resistance, etc. The disagreement among researchers
on the corrosion behaviour of these coatings warrants a thorough investigation. Among the various techniques available for
the determination of corrosion resistance, electrochemical impedance spectroscopy (EIS) is considered to be superior as it
provides not only an assessment of the corrosion resistance of different deposits but also enables the mechanistic pathway
by which the deposits become corroded to be determined. The present investigation focuses on the evaluation of the corrosion
resistance of electroless Ni-P and Ni-P-Si3N4, Ni-P-CeO2 and Ni-P-TiO2 composite coatings produced using an acidic hypophosphite-reduced electroless nickel bath, using EIS. The study makes evident
that the same fundamental reaction is occurring on all the coatings of the present study but over a different effective area
in each case. The charge transfer resistance of electroless Ni-P and Ni-P composite deposits are in the range 32,253–90,700 Ω cm2, whereas the capacitances of these coatings are in the range 11–17 μF/cm2. The improved corrosion resistance obtained for electroless Ni-P and Ni-P composite coatings is due to the enrichment of
phosphorus on the electrode surface, which enables the preferential hydrolysis of phosphorus over that of nickel. The better
corrosion resistance obtained for electroless Ni-P composite coatings can be ascribed to the decrease in the effective metallic
area prone to corrosion. Among the three electroless Ni-P composite coatings, the corrosion resistance is in the following
order: Ni-P-CeO2=Ni-P-Si3N4>Ni-P-TiO2.
Electronic Publication 相似文献
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EXAFS研究Ni-B和Ni-Ce-B超细非晶态合金的退火晶化 总被引:1,自引:0,他引:1
采用同步辐射EXAFS技术定量地研究化学还原法制备的Ni-B和Ni-Ce-B超细非晶态合金中Ni原子的局域环境结构随退火温度升高而产生的变化,结果表明,对于Ni-B和Ni-Ce-B超细非晶态合金初始样品:Ni-Ni最邻近配位壳层的平均键长RNi-Ni、配位数N、热无序σT、结构无序σs分别为0.275nm,11.9.0.0069nm,0.034nm;0.276nm,12.4,0.0067nm,0.035nm,Ni-B最邻近配位壳层的RNi-B,N, σT,σs分别为0.215nm,2.7,0.0055nm,0.0048nm;0.214nm,2.0,0.0058nm,0.0042nm,Ni-Ni配位的σs很大,是其σT的4-5倍,比Ni-B配位的σs大近一个数量级,在300℃退火后,Ni-B样品开始发生晶化生成晶态Ni3B,其RNi-Ni和σs分别为0.254nm和0.011nm,σs降低近2倍;而.3%原子比的Ce掺入后使Ni-Ce-B超细非晶态合金的晶化温度升高100℃左右。在500℃退火后,Ni-B样品的结构参数与Ni箔的相近,但Ni-Ce-B样品中的Ni-Ni配位的σs仍为0.0073nm,Ni-B配位的N为1.2,表明稀土元素Ce(以CeO2)显著增强了Ni与B的相互作用,且同时使退火晶化成的Ni晶结构产生畸变。 相似文献
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A. B. Drovosekov M. V. Ivanov V. M. Krutskikh Yu. M. Polukarov 《Russian Journal of Electrochemistry》2010,46(2):136-143
Catalytic activity, chemical composition, and structure of Ni-Re-B, Ni-Mo-B, and Ni-W-B alloys obtained by chemical-catalytic
reduction of metal ions were studied. Introduction of a doping element into the nickel-boron alloy changes the catalytic activity
of the alloy surface as regards concurrent partial reactions of heterogeneous hydrolysis of dimethylamine borane, reduction
of nickel atoms, evolution of molecular hydrogen, boron, and carbon. The aim of the work was to elucidate the causes for nonlinear,
bell-shaped dependence of partial rates of dimethylamine borane hydrolysis and hydrogen evolution on the concentration of
the doping element in the alloy. The structure and uniformity of distribution of elements in the coatings were evaluated.
Estimation of the grain size in the deposits based on the broadening of reflex (111) evidences the nanocrystalline structure
of the obtained alloys. The minimum grain size (<20 nm) corresponds to the doping element concentration within the alloy with
the maximum catalytic activity. Boron content in the alloys decreases at an increase in the doping element concentration.
The observed acceleration of the heterogeneous reaction of dimethylamine borane hydrolysis is explained by a change in the
catalytic activity of the coating surface as a result of the subsystem restructuring during the formation of an alloy between
nickel and the doping element. 相似文献
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负载型镍基非晶态催化剂催化氯代硝基苯加氢合成氯代苯胺 总被引:1,自引:0,他引:1
分别以碳纳米管(CNTs), SiO_2, TiO_2, γ-Al_2O_3, TiO_2-SiO_2和活性炭(AC)为载体(M),以Ni和B为活性组分,采用浸渍-化学还原法制备了一系列负载型Ni-B非晶态合金催化剂(Ni-B/M).采用电感耦合等离子体光谱(ICP), XRD, TEM和DSC研究了Ni-B/CNTs的非晶性质,Ni的担载量及其热稳定性.将Ni-B/M用于催化三种氯代硝基苯液相加氢合成氯代苯胺的反应.结果表明,Ni-B/M在反应中表现出较高的活性和良好的选择性,其中Ni-B/CNTs可使三种氯代硝基苯的转化率均高于99.8%,加氢脱氯率小于3%.讨论了CNTs和Ni-B之间的相互作用对催化剂性能的影响. 相似文献
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超细非晶镍合金的化学制备及类金属元素对性质的影响 总被引:8,自引:0,他引:8
常温下分别使用KBH4和NaH2PO2在水溶液中还原Ni^2^+制得了Ni65B35和Ni89P11超细非晶合金(UFAAP), 同时使用KBH4和NaH2PO2还原Ni^2^+制得了Ni73P13B14UFAAP. Ni-P的粒径较大, 约为110nm, Ni-B的粒径较小, 约为20nm,Ni-P-B的粒径居其之间, 约为40nm。XPS表明, Ni-P间的相互作用强于Ni-B间的相互作用, Ni-P-B中P的电子状态与Ni-P中的相似。Ni-P-B比Ni-P的比表面积高得多,Ni-P-B比Ni-B和Ni-P具有更好的非晶态稳定性, 在573K热处理, 它的非晶态保持完好。晶化结果也表明Ni-P-B中Ni-P间的相互作用比Ni-B间的强。 相似文献
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V. M. Krutskikh A. B. Drovosekov Yu. D. Gamburg A. D. Aliev B. F. Lyakhov V. M. Martynenko Yu. M. Shul’ga 《Russian Journal of Electrochemistry》2016,52(2):106-114
The data on the mechanism of electroless (catalytic) deposition of Co–Re–B coatings are obtained by determining the donor capacitance of dimethylamine borane (DMAB) (CH3)2HN · BH3 reductant and the oxidation level of its hydride hydrogen. From the results of the study of isotopic composition of evolved hydrogen, it is concluded that the oxidation level of DMAB hydride hydrogen depends on the catalytic activity of the alloy. The alloys containing up to 46 at % rhenium were produced by the electroless deposition. 相似文献
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非负载型磷化钼加氢精制催化剂的研制 总被引:9,自引:0,他引:9
尽管有相当多的文献和专利报道了含磷加氢精制催化剂的研究及磷的加入对Mn-Ni、Ni-Mo、Ni-W、Co-Mo、Mo、W、Ni、Co等各类加氢精制催化剂结构、及HDS、HDN活性的影响,并证明了磷或含磷化合物可作为加氢精制催化剂的助剂和稳定剂,但对于磷化物加氢催化剂的合成及对其HDS、HDN活性的研究还很少。本文在较低温度下用氢气直接还原磷钼酸铵盐得到非负载型的磷化钼催化剂,并以制备的磷化钼为活性组分,以SiC和γ-Al2O3为稀释剂,选择高浓度和低浓度的吡啶、噻吩和环己烯的混合物为模型化合物,以环己烷作溶剂,测定了制备催化剂的HDS、HDN及HYD活性。结果表明,所研制的非负载型磷化钼加氢精制催化剂对两种含有吡啶、噻吩和环己烯的模型化合物具有同时HDN, HDS 和 HYD的性能。 相似文献
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APTS改性SBA-15负载Ni-B非晶态合金催化加氢脱硫性能的研究 总被引:1,自引:1,他引:0
采用共价接枝法制备APTS改性介孔分子筛SBA-15,将氨基官能团接枝到SBA-15表面.并采用化学还原法制备了Ni-B/SBA-15-APTS非晶态合金催化剂,以噻吩加氢脱硫为探针反应,研究了其催化加氢脱硫性能.结果表明,240℃时,APTS改性SBA-15所负载的Ni-B催化剂噻吩转化率达到50.8%,较未改性SBA-15所负载的催化剂噻吩转化率有显著地提高.由于氨基与Ni2+的配合作用,有助于Ni在催化剂中的分散,因而更容易被还原.ICP结果表明,在相同的制备条件下,相比未改性的SBA-15,APTS改性SBA-15使其催化剂中Ni的负载量增加,并且非晶态合金组成中Ni的含量也增大,B的含量降低,有利于提高催化剂的活性. 相似文献
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M. P. Quiroga Argañaraz S. B. Ribotta M. E. Folquer G. Benítez A. Rubert L. M. Gassa M. E. Vela R. C. Salvarezza 《Journal of Solid State Electrochemistry》2013,17(2):307-313
This work reports on the features that Ni–W nanostructured alloys, electrodeposited on carbon steel by different current pulse programs, may present depending on their surface morphology and surface composition. The Ni–W nanostructured coating, with a cauliflower structure, lack of fragility, and high WO3/W surface composition ratio, is a stable electrode to catalyze hydrogen evolution reaction, exceeding bulk and electrodeposited Ni catalytic activity. Also, the nanostructured alloys must have a low WO3/W surface composition ratio for Ni and its oxides to provide protection and improve corrosion resistance in sulfate media. 相似文献
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以壳聚糖(CS)对SiO2进行表面修饰, 采用浸渍还原法制备了负载型Ni-B非晶态合金催化剂(Ni-B/CS/SiO2), 并采用XRD、FTIR、电感耦合等离子体发射光谱(ICP)、BET、XPS、TEM、SAED等表征方法研究了催化剂的非晶性质、原子组成、尺寸分布及粒径大小等. 考察了催化剂对糠醇加氢制四氢糠醇反应的催化性能, 并与没有壳聚糖修饰的Ni-B/SiO2催化剂及Raney Ni催化剂进行了对比. 结果表明, 加入壳聚糖制得的Ni-B/CS/SiO2催化剂的活性组分Ni-B团簇粒径更小, 表面活性组分浓度更高, 催化活性更高. 相似文献