多级结构FeS@Ni3S2/NF催化电极的一步水热法制备及析氧行为

通过简单一步水热法在泡沫镍表面原位生长多孔纳米片自组装成纳米花结构的FeS@Ni₃S₂/NF催化电极。借助X射线衍射仪(XRD)、X射线光电子能谱(XPS)、透射电镜(TEM)等进行物相及结构表征,并测试催化电极在1 mol/L KOH溶液中的电催化析氧(OER)性能。电化学测试结果表明：FeS@Ni₃S₂/NF-1.2电极在100 mA·cm-2电流密度下仅需278 mV的过电位,且具有较低的Tafel斜率(22.71 mV/dec),与纯NF(493 mV,214.65 mV/dec)、纯Ni₃S₂(327 mV,91.87 mV/dec)以及IrO2/NF(385 mV,172.93 mV/dec)相比,其优势明显。证明具有独特多孔结构的FeS@Ni₃S₂/NF纳米片自组装成的纳米花可以作为一种贵金属基电催化剂的理想替代品。     

磷酸盐前驱体对泡沫镍上生长的镍/铁羟基氢氧化物形貌及析氧反应性能的影响（英文）

通过共沉积法和电化学激活法在泡沫镍网上生长制备镍/铁羟基氢氧化物纳米片。研究发现,不同磷酸盐前驱体(Na₃PO₄、Na₂HPO₄和NaH₂PO₄)对最终催化剂的形貌及析氧反应活性有不同的影响。使用Na₂HPO₄制备的镍/铁羟基氢氧氯化物纳米片在1 mol/L KOH溶液中电流密度达到50 mA/cm²时所需过电位为205 mV,Tafel斜率低至30 mV/dec,并可以在后续稳定性测试中保持稳定20 h。     

钌基双金属聚酞菁电催化析氧性能研究

电解水制氢阳极电催化析氧反应(OER)动力学缓慢，可采用阳极OER催化剂提高。采用简单的低温热解法制备出钌(Ru)、铁钌(Fe Ru)和钴钌(CoRu)复合聚酞菁等一系列催化剂，通过X射线粉末衍射仪(XRD)、扫描电子显微镜(SEM)、X射线光电子能谱(XPS)对催化剂的形貌和结构进行表征，并采用电化学工作站对催化剂的析氧等电催化性能进行测试。测试结果表明，催化剂Fe₃Ru-PPc在碱性环境下电流密度为50 mA·cm^-2时的过电位为303.5 mV，塔菲尔斜率仅为42.3 mV·dec^-1，相比于商业Ir O₂具有更好的OER活性。对其结构分析可知，Fe与Ru的结合使得材料的电子结构发生变化，促进了OER的动力学过程，从而使其具有更好的OER活性和载流子迁移率。     

用于钯催化载体的P改性高孔隙率γ-Al2O3/α-Al2O3泡沫(英文)

提出了一种新方法来制备用于钯催化剂的P-γ-Al₂O₃涂层改性的α-Al₂O₃泡沫。采用聚氨酯模板法,通过优化工艺参数,使陶瓷泡沫的显气孔率达到90.28%,体积密度达到0.45 g·cm^-3,且该泡沫具有可使用强度。将掺有P元素的γ-Al₂O₃涂层涂覆在α-Al₂O₃泡沫上,然后通过超声波辅助浸渍法来装载活性催化相(Pd)。结果表明,含P涂层增加了惰性泡沫的比表面积和弱酸性位点,同时减少了强酸性位点的占比。与无涂层的泡沫相比,改性的泡沫更容易装载活性相,且装载的金属Pd不容易被氧化,CO的催化转化温度(T₅₀,T₉₀)降低了50℃左右。该研究证明了低成本改性α-Al₂O₃陶瓷泡沫在钯催化剂生产中具有极大的应用潜力。     

尿素调控纳米多孔合金NiFeCoMgCN的电催化性能

制备高效、稳定的析氧反应(OER)电催化剂是工业制氢的关键所在。使用尿素作为造孔剂和活性C/N源,基于纳米级柯肯达尔效应,通过高温烧结制备了纳米多孔合金NiFeCoMgCN,并分析了其作为电极的电催化性能。结果表明：在1 M KOH溶液中,NiFeCoMgCN电极在10 mA·cm^-2下的过电位为199 mV,Tafel斜率为41.7 mV·dec^-1,优于IrO₂/Ni foam电极(10 mA·cm^-2下的过电位为215 mV,Tafel斜率为76.3 mV·dec^-1),并且在1 A·cm^-2的大电流密度下能够持续工作至少100 h。NiFeCoMgCN电极优异的催化活性归功于其连续的纳米多孔结构和本质活性的提高。     

1,3-二甲基-2-咪唑啉酮-AlCl3-Cu2O离子液体电沉积金属铜

为找到一种电沉积金属铜的新方法,选用1,3-二甲基-2-咪唑啉酮(DMI)、AlCl₃和Cu₂O(摩尔比为90∶10∶4)的溶剂化离子混合液体进行铜的恒电位电沉积,并分析了电解质的离子结构、电导率、黏度和密度等。拉曼光谱和核磁共振分析表明DMI-AlCl₃-Cu₂O体系中存在[AlCl₂(DMI)₄]⁺、AlCl₃(DMI)₂和[AlCl₄]^-等离子团,DMI-AlCl₃-Cu₂O体系的电导率、黏度和密度随温度在323～373 K区间内呈线性变化。循环伏安研究表明,铜的起始还原电位为-0.4 V(vs Al),还原峰电位为-1.35 V;在-1.1 V至-1.4 V条件下恒电位电沉积得到金属铜,在-1.1 V和-1.4 V电位下电沉积得到的产物表面较平整,在-1.2 V和-1.3 V电位下电沉积得到的产物...     

高效析氢用花状MoSxSe2-x纳米复合材料的简便合成(英文)

为了解决MoSe₂导电性差和活性位点有限的问题，通过简便水热工艺合成具有缺陷的三元MoS_xSe_2-x纳米片。结果表明，硫元素的引入，不仅提高了其电子转移能力，而且提供了更多的电催化活性位点。因此，优化后S/Se摩尔比为1:1的MoS_xSe_2-x(MoSSe)具有优异的电催化析氢(HER)性能，其Tafel斜率仅为47 mV/dec，在-10 mA/cm²下具有较低的过电位(-165 mV)，并且具有良好的耐久性。这项工作为更好地理解多因素调控在设计和合成MoSe₂基催化剂以提高其电化学活性方面提供了一条额外的途径。     

掺杂Sn对V/UiO-66催化剂抗碱金属性能的影响

采用浸渍法,以UiO-66为载体,制备了V/UiO-66及改性Sn-V/UiO-66催化剂,并对催化剂的碱金属钾中毒进行了模拟,探讨了钒钛催化剂的反应机理和失活机理。结果表明,K负载后催化剂的晶型变化不大并且催化剂比表面积的变化呈现不规律波动。负载了碱金属以后,催化剂的金属氧化还原性能和表面酸量迅速降低,这是催化剂活性降低的主要原因。添加Sn能够增强VO_x与其他组分的相互作用,进而提高VO_x的可还原性及V⁵⁺的占比,使Sn-V/UiO-66催化剂表面的VO_x提供更多的酸性位点。中毒后的K-Sn-V/UiO-66催化剂仍然具有较高的总酸量和较强的氧化还原性,表明Sn-V/UiO-66催化剂具有优异的抗碱金属中毒能力。     

MoSe2/CoSe2异质结构的构筑及其电催化析氢性能

采用一步水热合成的方法在钼网(MF)上原位构筑MoSe₂/CoSe₂异质结构电催化剂。采用X射线衍射仪(XRD)、扫描电镜(SEM)、透射电镜(TEM)和X光电子能谱仪(XPS)等对MoSe₂/CoSe₂异质结构的物相和形貌进行了表征，并在1 mol/L KOH电解液中对该电催化剂的析氢反应(HER)性能进行了测试。结果表明：MoSe₂/CoSe₂@MF-2为枝状阵列异质结构，在电流密度为10 mA/cm²下，其过电势为172.3 mV,Tafel斜率为45.8 mV/dec,表现出良好的HER性能和结构稳定性。该异质结构电催化剂的成功构筑，为后续硒化物异质结及其在电催化中的应用提供了良好的思路和研究基础。     

锌电积用Pb-Ag阳极MnO2镀膜的电化学性能

锌电积用Pb-Ag阳极存在析氧过电位高、表面铅易电化学氧化溶解,造成阴极电锌品质低等突出问题,如何减少阳极的溶铅污染并提升其催化析氧活性、降低反应能耗,成为亟待解决的难题。本文在Pb-Ag阳极表面电沉积一层均匀、致密的MnO₂薄膜,采用SEM、XRD和ICP等对MnO₂催化层的表面微观形貌、晶体结构和溶液含铅量进行分析;采用CV、LSV、EIS和Tafel等对Pb-Ag/MnO₂阳极的析氧催化活性和耐腐蚀性能进行分析。结果表明：在MnSO₄-H₂SO₄溶液中,当循环速率为200 mL/min、温度为80℃时,以4 mA/cm²电沉积120 min制备的Pb-Ag/MnO₂镀膜电极具有最佳的催化析氧和耐蚀性能;PbAg阳极经优化镀膜后,50 mA/cm²时其析氧过电位由936 mV降低为648 mV,腐蚀电流密度由7.03μA/cm²降低至0.66μA/cm^2<...     

Effect of the thickness of the Ru-coating on a counter electrode on the performance of a dye-sensitized solar cell

A ruthenium (Ru) catalytic layer was assessed as the counter electrode (CE) in dye sensitized solar cells (DSSCs) by examining the effect of the Ru thickness on the DSSC performance. Ru films with different thicknesses (34, 46, 69 and 90 nm) were deposited on glass/fluorine-doped tin oxide (FTO) substrates as the CE by atomic layer deposition (ALD) at 250 °C using RuDi as the precursor and O₂ as the reaction gas. Finally, a 0.45 cm² DSSC of glass/FTO/TiO₂/dye(N719)/electrolyte(C6DMII, GSCN)/Ru CE structure was prepared. The properties of the DSSCs were examined by field emission scanning electron microscopy (FESEM), four-point-probe, cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), current-voltage (I–V), incident photon-to-current conversion efficiency (IPCE), and dark current measurements. FESEM showed that the crystallized Ru films had been deposited quite uniformly and conformally on the glass/FTO surface. The sheet resistance of the Ru film decreased with increasing Ru thickness. CV profiling revealed an increase in catalytic activity with increasing film thickness. The charge transfer resistance at the interface between the Ru-coated CE and electrolyte decreased with increasing Ru thickness. I–V profiling showed that the energy conversion efficiency was increased up to 3.40 % by increasing the Ru thickness. Moreover, the IPCE and dark current results showed the efficiency of the Ru-coated CE was comparable to that of a conventional platinum (Pt) CE.     

Ru(II) complexes containing dihydro-1,1,3,3-tetramethyl-7,8-diazacyclopenta[1]phenanthren-2-ol ligand: Synthesis and their electrochemiluminescent characteristics

A series of new ruthenium(II) complexes containing dihydro-1,1,3,3-tetramethyl-7,8-diazacyclopenta[1]phenanthren-2-ol (DTDP-OH) ligand, such as [Ru(DTDP-OH)_n(L)_3−n]²⁺ (L = 2,2′-bipyridyl (bpy), o-phenanthroline (o-phen), 2,2′-bipyridine-4,4′-dicarboaldehyde (bpy-(CHO)₂), 1,3-dihydro-1,1,3,3-tetramethyl-7,8-diazacyclopenta[1]phenanthren-2-one(DTDP), n = 1, 2, 3) were synthesized and their electrochemical and photophysical properties were studied. The synthesized Ru(II) complexes containing the DTDP-OH ligand showed strong MLCT absorptions at 420–487 nm. All the synthesized Ru(II) complexes containing the DTDP-OH ligand exhibited more intensive ECL emissions than the well-known [Ru(o-phen)₃]²⁺ does. In particular, the ECL intensities of [Ru(DTDP-OH)₂(o-phen)]²⁺ and [Ru(DTDP-OH)₂(bpy-(CHO)₂)]²⁺ were observed to be more than 2-fold greater than that of [Ru(o-phen)₃]²⁺.     

Electrochemical properties of spinel compound LiNi_（0.5）Mn_（1.2）Ti_（0.3）O_4 as cathode materials for lithium ion batteries

The electrochemical properties of spinel compound LiNi0.5Mn1.2Ti0.3O4 were investigated in this study.The chemicals LiAc·2H2O,Mn(Ac)2·2H2O,Ni(Ac)2·4H2O,and Ti(OCH3)4 were used to synthesize LiNi0.5Mn1.2Ti0.3O4 by a simple sol-gel method.The discharge capacity of the sample reached 134 mAh/g at a current rate of 0.1C.The first and fifth cycle voltammogram almost overlapped,which showed that the prepared sample LiNi0.5Mn1.2Ti0.3O4 had excellent good cycle performance.There were two oxidation peaks at 4.21 V and 4.86 V,and two reduction peaks at 4.55 V and 3.88 V in the cycle voltammogram,respectively.By electrochemical impedance spectroscopy and its fitted result,the lithium ion diffusion coefficient was measured to be approximately 7.76 × 10?11 cm2/s.     

Controllable morphology,size and inner structure of Ru particles prepared by spray-pyrolysis

Micro-spherical Ru particles with varied Brunauer-Emmett-Teller (BET) surface area (from 0.2 m²/g to 56 m²/g) were synthesized from (NH₄)₂RuCl₆ solution visa spray-pyrolysis methods. The morphology and size of as-synthesized Ru particles were controlled by the dry spraying treatment, while the inner structure of Ru particles was adjusted by the sintering process. The influences of sintered temperature on the inner structure of Ru particles were investigated. The microstructural transformation mechanisms of spray dried (NH₄)₂RuCl₆ particles during thermal decomposition were revealed. The as-synthesized Ru powder with low BET surface area (0.1963 m²/g) shows good sintering property, while the Ru powder with high BET surface area (56.2313 m²/g) shows excellent sulfur capacity. The powder technology can be applied to regulate the morphology, size and inner structure of particles.     

Ru-doped phosphorene for electrochemical ammonia synthesis

The electrochemical ammonia synthesis has attracted increasing attention due to its energy saving characteristics.However,developing novel electrocatalysts and their mechanism remain great challenges.Here,several transition metal(TM) atoms doped on phosphorene were studied as N₂ fixation electrocatalysts by using density functional theory(DFT) calculations.The results demonstrate that single Ru atom doped phosphorene shows an excellent catalytic activity for ammonia synthesis via the ...     

Ruthenium oxide for effective activation of aluminium sacrificial anodes: a new approach

Abstract

Ruthenium oxide, one of the excellent electrocatalysts having high conductivity and high chemical and thermodynamic stability, has been coated onto the surface of an electrode made from a Al–5 wt-%Zn alloy. The activated aluminium ion was able to diffuse through the porous catalytic hydrophilic layer. Ruthenium oxide coated Al–Zn alloy anodes displayed high open circuit potential and high closed circuit potential during galvanic exposure with mild steel cathodes. A galvanic efficiency as high as 86% with an actual current capacity of 2573 A h kg^-1 was achieved. The RuO₂ film underwent very little deterioration and a considerable mass of the ruthenium oxide film persisted on the anode surface, even after the electrode size had been reduced to one third of its original size owing to galvanic dissolution. These electrodes are economically efficient, as convenient to prepare, install and use as other conventional electrodes, are tolerable of very aggressive media and highly efficient, even under high galvanic current loads.     

Dual-wavelength dual-indicator catalytic kinetic spectrophotometry for determination of trace Ru(III)

A new dual-wavelength dual-indicator catalytic kinetic spectrophotometric method for the determination of trace Ru(III)was studied.This method was based on Ru(III)-catalyzing oxidation of Arsenazo I and indigo carmine by potassium bromate in sulfuric acid.The absorbances of the catalytic and noncatalytic systems were measured at 510 and610 nm,respectively.Under the optimum conditions,the linear range of determination is 0–0.12 lgáml-1and the detection limit is 1.21 9 10-4lgáml-1.The method was applied for the determination of trace Ru(III)in ore samples with satisfactory results.     

High-performance organic light emitting diodes fabricated with a ruthenium oxide hole injection layer

We report enhanced hole injection using an RuO_x layer between indium tin oxide anodes and 4,4′-bis[N-(1-naphtyl)-N-phenyl-amino]biphenyl in organic light emitting diodes (OLEDs). The operation voltage of OLEDs at a current density of 100 mA/cm² decreased from 17 V to 14 V and the maximum luminance value increased from 120 cd/m² to 2500 cd/m² upon transformation of the Ru layer to RuO_x by surface treatment using O₂ plasma. Synchrotron radiation photoelectron spectroscopy results showed that the work function increased by 0.4 eV as the Ru layer was transformed to RuOx. Thus, the hole injection energy barrier was lowered, reducing the turn-on voltage and increasing the quantum efficiency of the OLEDs.     

Enhanced hydrogen sorption properties in the LiBH4-MgH2 system catalysed by Ru nanoparticles supported on multiwalled carbon nanotubes

The LiBH₄-MgH₂ system has a high reversible hydrogen storage capacity. However, the hydrogen de/absorption kinetics has to be further enhanced for its practical application. Motivated by the possibility that the metal catalysts facilitating the dissociation and combination of hydrogen molecules and activating Mg-H and B-H bonds, a novel catalyst, ruthenium nanoparticles supported on multiwalled carbon nanotubes (Ru/C) is prepared and its effect on the hydrogen sorption properties of LiBH₄-MgH₂ systems is investigated. The experimental results show that the Ru/C catalyst is active in reducing the dehydrogenation temperature and enhancing the dehydrogenation kinetics. Furthermore, the reversible capacity is also markedly enhanced under moderate conditions, and the catalytically enhanced hydrogen absorption capacity persists well during three de/rehydrogenation cycles.     

The photovoltaic performance of new ruthenium complexes in DSSCs based on nanorod ZnO electrode

Three new heteroleptic ruthenium complexes, [Ru(L1)(dcbpy)(NCS)₂] Ru^II(4,7-diphenyl-1,10-phenanthroline-disulfonic acid disodium salt)(4,4′-dicarboxy-2,2′-bipyridyl)-di(thiocyanate) [K28], [Ru^II(L1)₂(NCS)₂] Ru^IIbis(4,7-diphenyl-1,10-phenanthroline-disulfonic acid disodium salt)-di(thiocyanate) [K313], and [Ru(L2)(dcbpy)(NCS)₂] Ru^II(1,10-phenanthroline-5,6-dione)(4,4′-dicarboxy-2,2′-bipyridyl)-di(thiocyanate) [K27], have been synthesized as sensitizers for dye-sensitized solar cells (DSSCs) using ZnO nanorod electrode. The photovoltaic performances of the solar cells based on these sensitizer dyes are studied under AM 1.5 irradiation (100 mW/cm²). Their photophysical and electrochemical properties are also investigated. ZnO nanorod based dye sensitized solar cell sensitized with K28 ruthenium complex bearing bulky sulfoxy groups gives an overall conversion efficiency of 2.51, a short-circuit current of 7.19 mA/cm², and an open circuit voltage of 550 mV. K28 is firstly designed and synthesized in the literature to increase molar extinction coefficients and enhanced spectral response in the visible light by expanding the π-conjugation, and of course to reduce back electron transfer due to the bulky sulfoxy groups. The vertical excitation energies, corresponding excitation wavelengths and oscillator strengths, predominant orbitals involved in ten singlet–singlet transitions and their characters obtained from the single point TD-DFT calculations have been obtained for K28.