Pd nanoparticles supported on CeO2 as efficient catalyst for hydrogen generation from formaldehyde solution at room temperature

A facile and efficient method for facilitating hydrogen generation from formaldehyde aqueous solution was developed using Pd nanoparticles supported on CeO₂ (Pd/CeO₂) as the catalyst. The prepared Pd/CeO₂ catalyst exhibited 100% H₂ selectivity and excellent catalytic activity for formaldehyde dehydrogenation with the initial rate of 2089 ml min⁻¹ g_Pd⁻¹ at room temperature and atmospheric pressure without any extra additive. The prepared catalyst was stable and reusable, and its catalytic activity kept almost unchanged after it was reused for the fifth run. Therefore, it is considered that this Pd/CeO₂ based hydrogen generation system may serve as an alternative hydrogen supply candidate for practical application.     

Three-dimensional nitrogen-doped graphene hydrogel supported Co-CeOx nanoclusters as efficient catalysts for hydrogen generation from hydrolysis of ammonia borane

Benefit from the strong synergistic electronic effect between Co and CeO_x, as well as the strong metalsupport interaction between Co-CeO_x and 3D NGH, the as-synthesized Co-(CeO_x)_0.91/NGH catalyst exhibits excellent catalytic activity toward hydrolysis of ammonia borane, with the turnover frequency (TOF) value of 79.5 min^-1.     

红毛丹状磷化钴@钼钴氧空心微米小球用于碱性电催化析氢（英文）

氢气因其能量密度高、零排放和可再生的特点被广泛认为是最有前景的能源.电解水是一种产生高纯氢气的有效途径.目前,高性能的促进水电解的催化剂主要是贵金属材料,例如贵金属铂.然而,高成本大大阻碍了贵金属材料在电催化水分解中的广泛应用.因此,我们致力于研究具有高活性的非贵金属催化剂.因为电催化水分解析氢反应更容易发生在质子浓度高的条件下,所以研究碱性条件下催化析氢比研究酸性条件下催化析氢更具挑战性.在工业应用中,酸性电解质溶液对仪器设备的腐蚀性比碱性溶液更大,因此研究应用在碱性溶液中的析氢催化剂更有发展前景.过渡金属磷化物被广泛地研究作为高性能析氢电催化剂,然而过渡金属磷化物作为析氢催化剂的稳定性通常不是很好.我们通过钼元素的引入,提高过渡金属磷化物作为析氢催化剂的稳定性.电化学催化效率同样受到材料形貌和导电性的影响.大的比表面积有利于暴露更多的活性位点,使活性位点与电解质溶液的接触更加充分,有利于催化剂和溶液之间的传质.据报道,金属磷化物具有良好的导电性是由于磷化物中存在金属-金属键.所以合成具有大比表面积形貌的过渡金属磷化物材料能够满足析氢电催化剂对比表面积和导电性的两个需求.界面效应是调节催化剂性能的一个有效方法.析氢催化剂常常存在吸附质子能力过强或过弱、稳定性不好等问题.这些问题可以通过界面效应来解决.本文通过形成磷化估和钼钴氧的界面来调节改善磷化钴表面原来的电子密度,以达到理想的氢吸附自由能;同时此界面效应还能起到稳定催化剂性能的作用.本文首先采用水热法合成了红毛丹状钼钴氧空心微米小球前驱体.在钼酸根离子的引导下,利用奥斯特瓦尔德熟化原理一步实现了红毛丹状空心结构.前驱体再以次亚磷酸钠为磷源进行气相磷化,得到产物红毛丹状磷化钴@钼钴氧空心微米小球.通过扫描电镜和透射电镜对其红毛丹状空心结构进行了表征.利用X射线衍射和X射线光电子能谱等手段表征了材料的物相组成和价态分布.电化学测试均使用电化学工作站完成.该材料在碱性电解质溶液中展现了极好的电化学催化析氢性能,在电流密度为10 mA cm^-2时对应的析氢过电位仅为62 mV.在1 MKOH溶液中10 mA cm^-2电流密度下测试55 h,过电位仅增大约17 mV,显示了非常强的碱性析氢稳定性.得益于磷化钴和钼钴氧之间的界面效应,以及特殊的三维空心结构,红毛丹状磷化钴@钼钴氧空心微米小球表现出优异的析氢催化性能和稳定性.     

A sensitive amperometric sensor for hydrazine and hydrogen peroxide based on palladium nanoparticles/onion-like mesoporous carbon vesicle

Onion-like mesoporous carbon vesicle (MCV) with multilayer lamellar structure was synthesized by a simply aqueous emulsion co-assembly approach. Palladium (Pd) nanoparticles were deposited on the MCV matrix (Pd/MCV) by chemical reduction of H₂PdCl₄ with NaBH₄ in aqueous media. Pd(X)/MCV (X wt.% indicates the Pd loading amount) nanocomposites with different Pd loading amount were obtained by adjusting the ratio of precursors. The particular structure of the MCV results in efficient mass transport and the onion-like layers of MCV allows for the obtainment of highly dispersed Pd nanoparticles. The introduction of Pd nanoparticles on the MCV matrix facilitates hydrazine oxidation at more negative potential and delivers higher oxidation current in comparison with MCV. A linear range from 2.0 × 10⁻⁸ to 7.1 × 10⁻⁵ M and a low detection limit of 14.9 nM for hydrazine are obtained at Pd(25)/MCV nanocomposite modified glassy carbon (GC) electrode. A nonenzymatic amperometric sensor for hydrogen peroxide based on the Pd(25)/MCV nanocomposite modified GC electrode is also developed. Compared with MCV modified GC electrode, the Pd(25)/MCV nanocomposite modified GC electrode displays enhanced amperometric responses towards hydrogen peroxide and gives a linear range from 1.0 × 10⁻⁷ to 6.1 × 10⁻³ M. The Pd(25)/MCV nanocomposite modified GC electrode achieves 95% of the steady-current for hydrogen peroxide within 1 s. The combination of the unique properties of Pd nanoparticles and the porous mesostructure of MCV matrix guarantees the improved analytical performance for hydrazine and hydrogen peroxide.     

Molybdenum-doped titanium dioxide supported low-Pt electrocatalyst for highly efficient and stable hydrogen evolution reaction

The Platinum(Pt)-based catalysts exhibit excellent catalytic performance for the hydrogen evolution reaction(HER) while suffering from poor stability due to the weak interaction between the carbon support and Pt.Herein,a molybdenum-doped titanium dioxide(Ti_(0.9)Mo_(0.1)O_2) supported low-Pt electrocatalyst with stronger interaction between catalyst and support is applied to tune the electrocatalytic performance of Pt.The Ti_(0.9)Mo_(0.1)O_2 support can not only tolerate the corrosion environment in the catalytic system,but also generate strong metal-support inte raction(SMSI) between the oxide and catalyst.A facile solvothermal method is used to prepare Ti_(0.9)Mo_(0.1)O_2 as support to anchor Pt nanoparticles.The 5% Pt supported on Ti_(0.9)Mo_(0.1)O_2 catalyst exhibits 4.4-fold mass activity(MA) at an overpotential of 50 mV and higher stability than 20% Pt/C with only 1/4 Pt loading.The SMSI between the Ti_(0.9)Mo_(0.1)O_2 and Pt prevents the Pt aggregation to achieve excellent stability,and hydrogen spillover effect in the interface between Pt and support benefits the hydrogen production process.This work presents a novel sight for the fabrication and design of oxide supported catalysts in various catalytic system by reasonably employing support effect.     

含金金属纳米颗粒用于液相化学氢化物催化制氢

液相化学氢化物以化学键的形式储存氢能,被认为是一类很有前景的化学储氢材料。液相化学氢化物的大规模应用很大程度上依赖于高效催化系统的开发。含金金属纳米颗粒在用于液相化学氢化物催化制氢中表现出优异的催化性能。本文综述了金纳米颗粒和含金异金属纳米颗粒用于液相氢化物催化制氢的最新研究进展。     

Ultrafine molybdenum carbide nanoparticles supported on nitrogen doped carbon nanosheets for hydrogen evolution reaction

Nitrogen doped carbon nanosheets supported molybdenum carbides nanoparticles (Mo_xC/NCS) have been synthesized by tuning the mass ratio of melamine and ammonia molybdate. The Mo₂C/NCS-10 exhibits superior electrocatalytic performance and stability for HER, which was attributed to N-doped carbon nanosheets, small particle size, mesoporous structure, and large electrochemical active surface area.     

弱磁性Co0.85Se纳米片负载碳纳米管作为电催化析氢催化剂

氢气是一种环境友好可再生的清洁能源,电解水无疑是一种很好的制氢方法.然而,电催化分解水析氢受到其缓慢的动力学过程、较低的催化性能和较差的稳定性的限制.为了使整个过程更节能,具有高电流密度和低的过电势的高效电催化剂被广泛研究.非化学计量相硒化钴(Co0.85Se)作为一种重要的金属硫属化合物具有优异的催化性能而广受关注.但是低维的Co0.85Se活性位点少,分散性差,电子传递能力低,导致其电催化剂活性差.多壁碳纳米管(MWCNTs)具有多种电性能,包括金属导电性和电子存储能力等.因此,MWCNTs的特殊结构和高导电性可以有效地促进电子从电催化剂向碳纳米管的转移,实现高效电分解水制氢性能.本文在不使用表面活性剂和模板的情况下,通过一步水热溶剂热法合成弱磁性Co0.85Se纳米片负载碳纳米管电催化剂.采用磁滞回线研究Co0.85Se和MWCNTs/Co0.85Se的磁性能,结果表明其有弱顺磁性,Co0.85Se纳米片之间的空间距离增强导致粒子间偶极相互作用减弱,从而使MWCNTs/Co0.85Se纳米复合材料的矫顽力值增加到158 Oe.随着微晶尺寸的减小和纳米颗粒间距的增大,MWCNTs/Co0.85Se催化剂的比表面积增大,有利于提高其电催化活性.扫描电镜和透射电镜展示出Co0.85Se纳米片分散性较差,且团聚现象严重,而MWCNTs/Co0.85Se纳米复合催化剂显示Co0.85Se纳米片均匀分散在MWCNTs表面,且纳米片尺寸明显减小,有利于Co0.85Se纳米片暴露更多的活性位点.线性扫描伏安曲线测量表明,在酸性溶液中Co0.85Se纳米片在电流密度为10 mA cm?2时,其过电势为319 mV(vs.RHE),30 wt%MWCNTs/Co0.85Se的过电势为266 mV(vs.RHE).Co0.85Se和MWCNTs/Co0.85Se的Tafel斜率分别为92.6和60.5 mV dec?1.此外,MWCNTs/Co0.85Se的电流交换密度(j0)为0.07 mA cm?2.较小的Tafel斜率和高的电流交换密度表明,MWCNTs/Co0.85Se具有良好的反应动力学和快速的质子分离速率.交流阻抗谱表明MWCNTs/Co0.85Se比Co0.85Se电阻更小,电子传输速率更快.电化学活性表面积与双电层在固液界面处的电容测量值成正比.结果显示,30 wt%MWCNTs/Co0.85Se的双电层电容为0.22 mF cm^-2,高于Co0.85Se和15 wt%的rGO/Co0.85Se(0.04 mF cm^-2,0.17 mF cm^-2),这表明较大的电化学活性表面积有利于析氢反应进行.30 wt%MWCNTs/Co0.85Se的循环稳定测试表明其具有较好的稳定性.综上,本文介绍了通过一步水热法合成具有弱磁性的Co0.85Se和MWCNTs/Co0.85Se电催化剂,碳纳米管作为一种高导电性材料被引入Co0.85Se纳米片中以减少Co0.85Se的团聚,使Co0.85Se的活性位点增加,进而提高电催化制氢性能.     

CeO2纳米管负载Pd纳米颗粒催化CO低温氧化

高效负载型Pd催化剂的制备及其在CO低温氧化反应中的机理探究是近年来的研究热点.普遍认为,Pd催化剂上的CO氧化反应遵循Langmuir-Hinshelwood机理:首先,CO吸附于Pd物种表面;然后,CO与催化剂表面的晶格氧发生反应转化为CO2,反应发生在金属-载体界面.另外,高分散的Pd活性物种有利于CO氧化反应.同时载体的形貌、暴露的晶面、氧空位以及孔结构等都是影响催化剂活性的重要因素.CeO2纳米管具有独特的管状特征和较高的比表面积,是一种潜在的CO低温氧化催化剂载体.本文利用乙醇还原法,以CeO2纳米管为载体,制备不同Pd含量的Pd/CeO2-nanotube纳米催化剂,并利用N2吸附脱附、X射线衍射(XRD)、透射电子显微镜(TEM)、CO程序升温脱附(CO-TPD)、X射线光电子能谱(XPS)等表征手段,探索纳米催化剂载体形貌对CO氧化反应活性的影响.氮气吸脱附结果表明,Pd/CeO2-nanotube具有较高的比表面积(58.0 m2/g),且存在介孔结构.XRD表征发现,Pd/CeO2-nanotube的衍射峰对应立方萤石型结构的CeO2的(111),(200),(220),(311)等品面.TEM结果表明,Pd/CeO2-nanotube具有均匀的纳米管形貌,其外径为40-60 nm,Pd纳米颗粒均匀分散在其表面.CO-TPD结果表明,Pd/CeO2-nanotube在1 10℃附近具有很强的脱附峰,在370℃和600℃附近分别具有较宽和较弱的脱附峰,这表明该催化剂具有较多的吸附位,且具有很强的CO吸附能力;CO不可逆吸附量计算结果表明,该催化剂上的Pd具有很高的表面分散度(23.3％),Pd颗粒尺寸为7.3 nm.XPS表征显示,Pd以pd2+的形式分散于CeO2纳米管的表面,且与载体发生相互作用,存在Pd-O-Ce键;同时该催化剂表面存在丰富的Ce3+,为反应提供更多的氧空位.0.9Pd/CeO2-nanotube纳米催化剂在CO氧化反应中表现出优良的活性,能在100℃实现CO的完全转化;通过计算发现,该催化剂具有较高的TOF值(0.63 s-1),由Arrhenius 曲线可得到该催化剂的活化能为26.5 kJ/mol.综上可见:金属活性组分的尺寸和分散度、载体的结构特征、CO吸附能力以及金属-载体间的相互作用决定催化剂的性能.Pd/CeO2-nanotube的高比表面积有利于Pd的分散;其强CO吸附能力有利于CO吸附于Pd物种表面;催化剂表面丰富的Ce3+能为反应提供更多的氧空位,Pd-O-Ce键的形成能增强金属-载体间的相互作用,有利于CO与催化剂表面品格氧发生反应.同时催化剂介孔结构有利于反应气体和产物气体的吸附和扩散,因此,Pd/CeO2-nanotube纳米催化剂在CO氧化反应中表现出优良的活性.     

Pt/Cu双金属纳米颗粒的制备及其催化制氢活性

采用化学共还原法合成了聚乙烯吡咯烷酮保护的Pt/Cu双金属纳米颗粒(BNPs),并采用紫外可见吸收光谱、透射电子显微镜、高分辨透射电子显微镜等对所合成的Pt/Cu BNPs进行了表征。研究了化学组成对Pt/Cu BNPs催化Na BH4水解制氢性能的影响。结果表明,所制备的Pt/Cu BNPs平均粒径为1.8~2.3nm,其催化活性远高于单金属Pt和Cu NPs的活性,其中Pt90Cu10BNP的催化活性最高,其在30℃的条件下,催化Na BH4制氢的活性可达6570mol-H2·mol-cat-1·h-1,约为相同粒径的Pt单金属NP的1.6倍。密度泛函理论的计算结果表明,Pt/Cu BNPs优异的催化性能可归因于电荷转移效应,Pt原子与Cu原子之间发生的电子转移使得Pt原子带负电而Cu原子带正电,荷电的Pt和Cu原子成为催化反应的活性中心。     

Silver-Cobalt bimetallic nanoparticles to the generation of hydrogen from formic acid decomposition

The fabrication of cost effective heterogeneous catalysts for the release of hydrogen from hydrogen storage materials is the key technological challenge to the fuel-cell based hydrogen economy. Ag-Co bimetallic NPs were fabricated by using sodium dodecyl sulphate (SDS) and sodium borohydride as stabilizing and reducing agents, respectively. Catalytic activity of SDS-Ag-Co was higher than that of SDS free Ag-Co and monometallic (Ag and Co) due to the electron interactions and synergistic effect between the Ag and Co. Ag₁₀-Co₉₀ exhibited the superior catalytic activity, with rate constant of 5.2 × 10^?4 s^?1 at 303 K, activation energy of 46 kJ/mol, activation enthalpy of 44 kJ/mol, activation entropy of ?165 J/K/mol, and turn over frequency of 240 h^?1. The hydrogen generation rate increased and decreased with in increasing temperature, molar concentration of formic acid, presence of sodium formate, and pH, respectively. The kinetic rate equation can be stated as: rate = -d[formic acid]/dt = k_obs[formic acid]^0.99[Ag₅₀Co₅₀]^0.98, k_obs = 2.48 × 10⁷ exp (?5637.96/RT).     

高效 CeO2-MnOx-Al2O3催化剂的制备、表征及催化消除 NO性能

机动车在给人类生活带来便利的同时,也造成了严重的大气污染.其尾气净化成为人们关注的焦点.一氧化氮(NO)、一氧化碳(CO)和碳氢化合物(HCs)是机动车尾气中的三大典型污染物,主要通过三效催化(TWC)技术进行脱除. TWC技术涉及几个重要的催化反应,其中 CO催化还原 NO由于能够同时消除 CO和 NO两种污染物而引起研究者的极大关注.研究表明,负载型贵金属催化剂在该反应中显示出优异的催化性能,但存在资源匮乏、价格昂贵以及热稳定性欠佳等不足.因此,低价、高效的过渡金属氧化物催化剂成为近年研究重点.稀土金属氧化物 CeO2由于具有良好的氧化还原性能、较高的储释氧容量以及丰富的表面氧空位而被广泛用于 CO催化还原 NO反应.研究表明,对 CeO2进行离子掺杂可进一步增大其比表面积,改善其氧化还原性能和储释氧容量.并且,我们在先前的研究中还发现,将具有多种可变价态的钛离子或锡离子掺入 CeO2晶格由于掺杂离子能与 Ce4+/Ce3+发生电子转移而更有利于改善 CeO2的理化性质.此外,锰氧化物(MnOx)在氧化还原气氛中容易实现不同价态之间的切换,从而在一些重要的氧化还原反应中表现出优异的催化性能.近年来,有研究者将 CeO2与 MnOx相结合制备了 CeO2-MnOx催化剂用于 NO消除、碳烟燃烧和挥发性有机物(VOCs)氧化等反应,并取得一些有意义的结果.然而,对于实际应用来说, CeO2-MnOx催化剂存在比表面积偏小等不足.众所周知,γ-Al2O3是一种常用的具有高比表面积和高热稳定性的催化剂载体材料,可有效增大催化剂比表面积.我们前期研究结果表明,通过共沉淀法将 Al3+掺入铈基复合氧化物的晶格相比于以γ-Al2O3为载体更有利于改善铈基复合氧化物的理化性质和催化性能.因此,我们通过简单的氨水反滴加共沉淀法制备了一系列 CeO2-MnOx-Al2O3(Ce：Mn：Al摩尔比=6：4：x,x =0.25,0.5,1,2)复合氧化物催化剂用于 CO催化还原 NO反应.并运用 X射线衍射、拉曼光谱、氮气物理吸附、氢气程序升温还原、X射线光电子能谱以及原位漫反射红外光谱等表征技术对上述催化剂进行了系统分析.重点考察了 Al3+掺杂量对 CeO2-MnOx-Al2O3复合氧化物催化剂理化性质和催化性能的影响.结果表明,在 CeO2-MnOx复合氧化物中掺入少量 Al3+会导致其晶粒尺寸减小,从而增大其比表面积和孔体积,并增加 Ce3+和 Mn4+的含量.比表面积和孔体积增大有助于催化剂与反应物分子之间充分接触; Ce3+和 Mn4+含量增加能分别促进 CO物种吸附以及吸附态 NO物种脱附、转化和解离.这些变化有利于提高 CeO2-MnOx复合氧化物在 CO催化还原 NO反应中的催化性能.最后,基于催化剂的理化性质表征及其催化性能评价,我们尝试提出了一个可能的催化反应机理,以进一步理解 CeO2-MnOx-Al2O3复合氧化物催化剂在 CO催化还原 NO反应中的优异性能.     

Plasma-modified iron-doped Ni3S2 nanosheet arrays as efficient electrocatalysts for hydrogen evolution reaction

The development of efficient transition-metal catalysts for the hydrogen evolution reaction is significant to meeting global energy demands. In this study, to realize a high-performance electrocatalyst, we synthesize an Fe-doped Ni₃S₂ nanosheet material in situ on 3D structured nickel foam via the hydrothermal sulfide method, and then modify it by the dielectric barrier discharge plasma technique. Combining Fe atom doping and plasma modification increases the electrochemical surface area, provides an abundance of active sites, optimizes the electronic structure, and accelerates the reaction kinetics, thereby improving catalytic activity. As a result, the PA@Fe_1/4-Ni₃S₂/NF catalyst exhibits excellent hydrogen evolution reaction activity, only requires ultra-low overpotentials to achieve a current density of 10 mA cm^?2, and exhibits excellent durability. This study proposes a novel method for rationally designing non-noble metal electrocatalysts.     

Study on kinetics and mechanism of copper-catalyzed oxidation of hydrazine by iron (III) in acid solution

The copper-catalyzed oxidation of hydrazine by iron(III) in acid solution follows the rate law -d[Fe(III)]/dt = kK_h[Cu(II)]²/(K_h + [H⁺]), where K_h is the hydrolysis constant of Cu²⁺, k was found to be 8.8±0.8, 13.2±1.4 and 17.5±1.3 min^?1 at 35, 40, and 45°C respectively and μ= 0.2 mol/L. The composition of the activated complex is Cu²⁺, CuOH⁺, N₂H₄, H⁺ or others. Perhaps several hydrazine complexes of Cu(II) participate in the reaction and one of them isolated was Cu(N₂H₄)₂(HSO₄)₂. Study on the oxidation of this complex is also in conformity with the above rate law.     

单分散Ni簇锚定在CN上用于高效光催化析氢

利用太阳光在常温常压下驱动光催化反应高效进行是解决人类面临的能源、环境问题从而实现绿色化学的理想方案之一.然而,兼顾效率、成本和稳定性的高性能光催化体系的研究依然存在巨大的挑战.石墨氮化碳(g-C3N4)基光催化剂由于高稳定性、无毒无害和适合的能带结构,在光催化制氢方面存在巨大潜力.然而,表面的慢反应速率导致了光生电子...     

Intrinsic catalytic structure of gold nanoparticles supported on TiO2

Despite the fragility of TiO(2) under electron irradiation, the intrinsic structure of Au/TiO(2) catalysts can be observed by environmental transmission electron microscopy. Under reaction conditions (CO/air 100?Pa), the major {111} and {100} facets of the gold nanoparticles are exposed and the particles display a polygonal interface with the TiO(2) support bounded by sharp edges parallel to the 〈110〉 directions.     

Green laser ablation-based synthesis of functional nanomaterials for generation,storage, and detection of hydrogen

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氮掺杂碳包埋钴纳米粒子电催化合成过氧化氢

电催化还原氧是一种新兴的可持续生产过氧化氢(H2O2)的合成技术,寻找低成本、高活性和高选择性的电催化剂是该技术实际应用的关键.钴氮掺杂的碳材料因含有钴氮(Co-Nx)催化活性位,成为一类新兴的可促进H2O2电化学合成的材料.本文采用低能耗干式球磨外加控制热解的方法来制备包含许多Co-Nx结构的钴氮掺杂碳材料.该方法使用材料廉价,即将醋酸钴、2-甲基咪唑和Ketjenblack EC-600JD高纯度且导电的碳黑分别作为金属、氮和碳的前体.在酸性介质中的电化学测试结果表明,该材料的氧还原反应电流密度明显增加,同时起始电位向正方向移动.该催化剂在较大电位范围内对H2O2的选择性约为90％.H2O2整体电解实验表明,H2O2产率达到100mmol gcat?1 h?1,H2O2法拉第效率达到85％(0.3Vvs.RHE条件下2h).耐久性测试(在0.3Vvs.RHE条件下6h)表明,催化剂表现出相对稳定的性能,且在整个测试循环中,法拉第效率达到约85％,表明催化剂在实际应用中具有良好的耐久性.催化剂表现出较高的电催化合成H2O2活性和选择性可能是由于形成了Co-Nx活性位,以及酸性环境和应用电位等其它因素的影响.