Interface engineering for enhancing electrocatalytic oxygen evolution reaction of CoS/CeO2 heterostructures

To realize renewable energy conversion,it is important to develop low-cost and high-efficiency electrocatalyst for oxygen evolution reaction.In this communication,a novel bijunction CoS/CeO₂ electrocatalyst grown on carbon cloth is prepared by the interface engineering.The interface engineering of CoS and CeO₂ facilitates a rapid charge transfer from CeO₂ to CoS.Such an electrocatalyst exhibits outstanding electrocatalytic activity with a low overpotential of 311 mV at 10 mA·cm?2 and low Tafel slope of 76.2 mV·dec?1,and is superior to that of CoS(372 mV)and CeO₂(530 mV)counterparts.And it has long-term durability under alkaline media.     

Ir-based oxide electrodes: oxygen evolution reaction from mixed solvents

The influence of 30% (v/v) organic cosolvent in 1.0 mol dm^–3 HClO₄ on the OER electrode kinetics, surface properties and electrode stability of IrO₂-based electrodes was investigated by cyclic voltammetry and polarization curves. The Tafel coefficients in the presence of cosolvent are explained in terms of the change of the rate-determining step (r.d.s.) of the OER electrode mechanism, coating dissolution and/or cosolvent oxidation. Of the several cosolvents investigated t-BuOH and PC show less effects on the OER and electrode properties making them the best choice for organic eletrosynthesis applications, in contrast to AN, which causes coating dissolution, and DMF and DMSO which show an anticipation of the voltammetric current.     

Recent advance in transition metal oxide-based materials for oxygen evolution reaction electrocatalysts

Using renewable energy to electrolyze water to produce hydrogen is the only way to realize a green hydrogen economy. At present, the large-scale application of this technology is encumbered by the relatively low activity and stability of oxygen evolution reaction (OER) electrocatalysts. The use of cost-effective catalysts can significantly reduce the overpotential of oxygen evolution and improve the economics and power conversion efficiency of the hydrogen production process from electrolysis of water. Among the various candidates, the transition metal oxide-based (TMOs) materials show great prospects and receive ever-increasing research interests because of their diversified surface/bulk structures, natural enrichment, easy accessibility and environmental friendliness. In this review, the latest tactics aiming at enhancing activity via increasing the accessible active sites and promoting intrinsic activity have been summarized. In addition, with special emphasis on the long-term stability, the up-to-data strategies for elevating the stability are introduced. Finally, conclusions and perspectives are also presented.     

过渡金属氧化物催化析氧反应研究进展

利用可再生能源电解水制氢,是实现绿色氢能经济的必由之路。现阶段,电解水过程的阳极析氧反应过电位较高,催化剂性能不稳定,制约着该技术的工业化应用。使用经济高效的催化剂,可显著降低析氧过电位,提高电解水制氢过程的经济性和电能转化效率。在各类析氧催化剂材料中,过渡金属氧化物(TMOs)由于晶体结构多样、储量丰富、环境友好、易于制备以及活性较高等优点,受到了越来越多的关注。本文从活性和稳定性出发,总结分析了近年来过渡金属氧化物催化析氧反应的研究进展,并对其未来的发展提出了建议与展望。     

快速界面法制备FeOOH@CoNi-LDH@NF用于高效析氧

以六水合硝酸钴、六水合硝酸镍、尿素和氟化铵为原料,采用水热法在镍网上原位构筑层状双金属氢氧化物(LDH)(CoNi-LDH@NF),然后采用快速界面法在硝酸钠和六水合氯化铁的100℃溶液中对其进行刻蚀制备了FeOOH@CoNi-LDH@NF.利用XRD、SEM、XPS和TEM对FeOOH@CoNi-LDH@NF进行了形...     

Heterometallic cluster-based organic frameworks as highly active electrocatalysts for oxygen reduction and oxygen evolution reaction: a density functional theory study

Recently, metal–organic frameworks are one of the potential catalytic materials for electrocatalytic applications. The oxygen reduction reaction and oxygen evolution reaction catalytic activities of heterometallic cluster-based organic frameworks are investigated using density functional theory. Firstly, the catalytic activities of heterometallic clusters are investigated. Among all heterometallic clusters, Fe₂Mn–Mn has a minimum overpotential of 0.35 V for oxygen reduction reaction, and Fe₂Co–Co possesses the smallest overpotential of 0.32 V for oxygen evolution reaction, respectively 100 and 50 mV lower than those of Pt(111) and RuO₂(110) catalysts. The analysis of the potential gap of Fe₂M clusters indicates that Fe₂Mn, Fe₂Co, and Fe₂Ni clusters possess good bifunctional catalytic activity. Additionally, the catalytic activity of Fe₂Mn and Fe₂Co connected through 3,3′,5,5′-azobenzenetetracarboxylate linker to form Fe₂M–PCN–Fe₂M is explored. Compared with Fe₂Mn–PCN–Fe₂Mn, Fe₂Co–PCN–Fe₂Co, and isolated Fe₂M clusters, the mixed-metal Fe₂Co–PCN–Fe₂Mn possesses excellent bifunctional catalytic activity, and the values of potential gap on the Mn and Co sites of Fe₂Co–PCN–Fe₂Mn are 0.69 and 0.70 V, respectively. Furthermore, the analysis of the electron structure indicates that constructing a mixed-metal cluster can efficiently enhance the electronic properties of the catalyst. In conclusion, the mixed-metal cluster strategy provides a new approach to further design and synthesize high-efficiency bifunctional electrocatalysts.     

非晶态硼化物Ni-Fe-Co-B的合成及电催化析氧性能

电解水制氢是绿色氢能源研究中的热点课题。其中，析氧半反应较高的过电位是导致电解水动力学缓慢的主要原因。为了提高电解水制氢的效率，本文主要通过简单的液相合成方法，以硼氢化钠和过渡金属Ni，Fe，Co盐为原料，制备了非晶态的过渡金属硼化物Ni-Fe-Co-B，将其作为析氧半反应催化剂。对Ni-Fe-Co-B进行了SEM、TEM、XRD、XPS和电化学表征。结果表明，非晶态催化材料Ni-Fe-Co-B被成功合成，当n(Ni)∶n(Fe)∶n(Co)=1∶1∶1，电流密度为20 mA/cm2时，Ni-Fe-Co-B的过电位仅为299 mV，Tafel斜率为101 mV/dec。在0.47 V的恒电压测试下，Ni-Fe-Co-B具有12h以上的稳定性。     

Oxygen-deficient MoOx/Ni3S2 heterostructure grown on nickel foam as efficient and durable self-supported electrocatalysts for hydrogen evolution reaction

High-performance and ultra-durable electrocatalysts are vital for hydrogen evolution reaction (HER) during water splitting. Herein, by one-pot solvothermal method, MoO_x/Ni₃S₂ spheres comprising Ni₃S₂ nanoparticles inside and oxygen-deficient amorphous MoO_x outside in situ grow on Ni foam (NF), to assembly the heterostructure composites of MoO_x/Ni₃S₂/NF. By adjusting volume ratio of the solvents of ethanol to water, the optimized MoO_x/Ni₃S₂/NF-11 exhibits the best HER performance, requiring an extremely low overpotential of 76 mV to achieve the current density of 10 mA∙cm^‒2 (η₁₀ = 76 mV) and an ultra-small Tafel slope of 46 mV∙dec^‒1 in 0.5 mol∙L^‒1 H₂SO₄. More importantly, the catalyst shows prominent high catalytic stability for HER (> 100 h). The acid-resistant MoO_x wraps the inside Ni₃S₂/NF to ensure the high stability of the catalyst under acidic conditions. Density functional theory calculations confirm that the existing oxygen vacancy and MoO_x/Ni₃S₂ heterostructure are both beneficial to the reduced Gibbs free energy of hydrogen adsorption (|∆G_H*|) over Mo sites, which act as main active sites. The heterostructure effectively decreases the formation energy of O vacancy, leading to surface reconstruction of the catalyst, further improving HER performance. The MoO_x/Ni₃S₂/NF is promising to serve as a highly effective and durable electrocatalyst toward HER.     

Multifunctional catalysts for de-NOx processes: The case of H3PW12O40·6H2O-metal supported on mixed oxides

The role of a multifunctional catalyst for de-NO_x process has been investigated. The NO_x storage capacity of H₃PW₁₂O₄₀·6H₂O (HPW) was improved by the presence of a noble metal (Pt, Rh or Pd). Both HPW and noble metal were deposited on a specific support (based on Zr–Ce or Zr–Ti). The presence of noble metal in several oxidation states, as evidenced by TPR and IR, involves the possibility of forming different catalytic sites: (i) M⁰ (zero-valent metal) and perhaps (ii) (metal–H)^δ+ from specific interactions between noble metal and the HPW proton. Supports were also able to adsorb and activate NO_x and to generate cationic catalytic sites (M^x+). These cationic sites seem to be the clue for their important activity toward NO_x reduction. This catalyst presents an outstanding resistance to SO₂ poisoning which can be related to NO and NO₂ absorption mechanism in HPW. The use of alternating short cycles of lean/rich mixtures allows us optimising the performance of this catalytic system in terms of both NO_x reduction capacity and NO_x storage efficiency: up to 48 and 84%, respectively (with a 2% CO + 1% H₂ mixture for reducing). Experimental results sustain two hypotheses: first, HPW-metal-support catalyst includes several (independent) catalytic functions required for a de-NO_x process to occur and second, the formation of oxygenate active species must be indispensable for NO_x reduction into nitrogen.     

Effect of the partial replacement of Fe by Ni and/or Mn on the electrocatalytic activity for oxygen evolution of the CoFe2O4 spinel oxide electrode

The study of the electrochemical behaviour of mixed spinel oxide electrodes, obtained by the partial replacement of Fe by Ni and/or Mn in the cobalt ferrite CoFe₂O₄ is presented. The electrodes were prepared by brush painting of iron substrates with a suspension of the respective oxide, prepared by solid-state reaction. The influence of the substituent on the electrodes electrocatalytic activity towards the OER is analysed in terms of the kinetic parameters obtained by steady state measurements and the cationic distribution proposed for the oxides. The data show that the introduction of Ni brings about the presence of Co³⁺ tetrahedrally coordinated in addition to the Co³⁺/Co²⁺ couple in octahedral sites, giving rise to a better electrocatalyst for the OER. In contrast the presence of Mn produces electrodes with lower catalytic activity.     

On the mechanism and energetics of Boudouard reaction at FeO(1 0 0) surface: 2CO→C+CO2

We present a density functional study on the mechanism of metal dusting at surfaces of transition metal oxides. The present study focuses on one of the major metal dusting processes: the Boudouard reaction on FeO(1 0 0) surface. Cluster models are used to represent the surface and the effects of cluster sizes and relaxation upon CO adsorption are carefully examined. It is found that the CO adsorption on a well-aligned transition metal oxide surface is very weak and does not lead to CO-bond dissociation. A minimum energy path of a gas-phase CO attacking an adsorbed CO from the surface normal is calculated and the structural change of the reaction species along the reaction path is examined. The results suggest that the Boudouard reaction is extremely unfavorable energetically at the transition metal oxide surfaces and that a pitting mechanism dictates the dusting process, in agreement with practical observations.     

MoVW mixed metal oxides catalysts for acrylic acid production: from industrial catalysts to model studies

(MoVW)₅O₁₄-type oxides were identified as the active and selective components in industrial acrylic acid catalysts. Tungsten is suggested to play an important role as a structural promoter in the formation and stabilization of this oxide. Vanadium is responsible for high catalytic activities but is detrimental for the stability of this oxide at the necessary high concentrations for optimum catalytic performance. The activity of mixed MoVW oxide catalysts for methanol, propene, and acrolein partial oxidation could be considerably improved, when the amount of the (MoVW)₅O₁₄-type oxide was increased by thermal annealing. A model is proposed on the basis of the correlation between Raman wavenumber and bond order and degree of reduction, which explains the observed different selectivities of MoO_3−x and the (MoVW)₅O₁₄-type oxides in terms of metal–oxygen bond strengths, i.e. oxygen basicity and oxygen lability, respectively. According to this model, the (MoVW)₅O₁₄ mixed oxide catalyses partial oxidation because of its intermediate C–H activation and oxygen releasing oxygen functionalities. However, these (MoVW)₅O₁₄-type industrial oxidation catalysts are heterogeneous and highly complex systems. Their physicochemical characterization also revealed that their chemical bulk and surface compositions vary with thermal activation and oxygen potential. A core-shell model is suggested to describe the active catalyst state, the shell providing a high number of active centers, the core high electronic conductivity and ion mobility. The fact that the surface composition of such catalysts is considerably different from their bulk compositions, most probably implies that the “molecular structure” at their surface differs too considerably from their bulk crystal structure. Hence, the posed question about the active catalyst structure and its relation to its catalytic performance cannot unambiguously be explained by the crystallographic structure, but still remains unsolved.     

In situ polarized total-reflection fluorescence X-ray absorption near-edge structure spectroscopy for the analysis of oriented structure of vanadium oxides on ZrO2(100)

The oriented structure of the exposed V=O bond of vanadium oxides on ZrO₂(100) was studied by in situ polarized total-reflection fluorescence X-ray absorption near-edge structure (XANES) spectroscopy. The pre-edge peak intensity of s-polarized XANES was half the intensity of the p-polarized one. Moreover, both pre-edge peaks decreased in a similar way and eventually became zero by the reaction of V=O bonds with NH₃ at 423 K, suggesting that all of the observed V=O bonds behaved as active sites. The present technique suggests that the exposed V=O bonds are oriented to a 45°-direction from the normal to the ZrO₂(100) surface.     

Microstructural characterization and phase analysis of new pyrochlore-type mixed metal oxides RESmTi2O7 (RE = Gd,Er) by X-ray powder diffraction using Rietveld refinement method and spectroscopic studies

Two new RESmTi₂O₇ mixed metal oxides were prepared by mixing Sm₂O₃, RE₂O₃ (RE = Gd, Er) and TiO₂ using a modified solid state method which gives the target pyrochlores with excellent phase purity. SmGdTi₂O₇ and SmErTi₂O₇ samples were characterized using PXRD, SEM, EDS, FT-IR and Raman spectroscopy. Rietveld refinement was employed to obtain crystallographic parameters using MAUD software. The qualitative phase analysis showed that the mixed metal oxides were crystallized in a cubic crystal system with the Fd3m space group with small shifting in Bragg positions due to the effect of RE cationic radius on the lattice structure. The quantitative phase analysis using Rietveld refinement method illustrated the relation between crystallographic parameters, structural factors and ionic radii of RE atoms, during which, the sensitivity of the pyrochlores for cationic radius variations of RE atoms, and the extraordinary effect of the RE on the crystal structure of pyrochlores were confirmed.     

A CTAB-assisted hydrothermal synthesis of VO2(B) nanostructures for lithium-ion battery application

Nanostructured VO₂(B) was synthesized via a combined hydrothermal method using V₂O₅ as a source material and oxalic acid powder as a reductant. Especially, cetyltrimethylammonium bromide (CTAB) was used as template and then three different morphologies of the VO₂(B): nanobelts, nanoflowers and nanoflakes were obtained through the change of the experimental conditions. The morphology and crystalline structure of the prepared products were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared spectroscopy (FTIR). Furthermore, the electrochemical charge–discharge cycling properties of the VO₂(B) nanostructures in lithium-ion battery were investigated. The results indicated that the belt-like, flower-like and flake-like VO₂(B) nanostructures have the initial specific discharge capacity of 205.2, 254.0 and 56.0 mA h g⁻¹, and that the morphology of VO₂(B) nanostructures can deeply affect the service performance of batteries. According to the experiments, this CTAB-assisted hydrothermal method provides an insight into the preparation and application of nanostructured VO₂(B) as cathode material in lithium-ion battery.     

Structure evolution of nanocrystalline CeO2 and CeLnOx mixed oxides (Ln = Pr, Tb, Lu) in O2 and H2 atmosphere and their catalytic activity in soot combustion

This paper reports results of studies on structure and activity in soot combustion of nanocrystalline CeO₂ and CeLnOx mixed oxides (Ln = Pr, Tb, Lu, Ce/Ln atomic ratios 5/1). Nano-sized (4–5 nm) oxides with narrow size distribution were prepared by a microemulsion method W/O. Microstructure, morphology and reductivity of the oxides annealed up to 950 °C in O₂ and H₂ were analyzed by HRTEM, XRD, FT-IR, Raman spectroscopy and H₂-TPR. Obtained mixed oxides had fluorite structure of CeO₂ and all exhibited improved resistance against crystal growth in O₂, but only CeLuOx behaved better than CeO₂ in hydrogen.

The catalytic activity of CeO₂, CeLnOx and physical mixtures of CeO₂ + Ln₂O₃ in a model soot oxidation by air was studied in “tight contact” mode by using thermogravimetry. Half oxidation temperature T_1/2 for soot oxidation catalysed by nano-sized CeO₂ and CeLnOx was similar and ca. 100 °C lower than non-catalysed oxidation. However, the mixed oxides were much more active during successive catalytic cycles, due to better resistance to sintering. Physical mixtures of nanooxides (CeO₂ + Ln₂O₃) showed exceptionally high initial activity in soot oxidation (decrease in T_1/2 by ca. 200 °C) but degraded strongly in successive oxidation cycles. The high initial activity was due to the synergetic effect of nitrate groups present in highly disordered surface of nanocrystalline Ln₂O₃ and enhanced reductivity of nanocrystalline CeO₂.     

TayNb1−yVO5 (0<y<1) mixed oxides synthesized by sol–gel method: electrochemical Li-insertion

Mixed oxides of general formulae Ta_yNb_1−yO₅ (0<y<1) have been synthesized by a modified sol–gel method. Characterization of the samples has been carried out by x-ray diffraction, SEM/EDX, FTIR spectroscopy and thermal analysis. The electrochemical properties have been studied in a lithium cell. The first discharge capacity decrease from 206 (y=0.25) to 136 mA h g⁻¹ (y=0.75). Ta_yNb_1−yO₅ samples undergo an irreversible structural changes induced by electrochemical Li⁺-insertion. For all compositions, the new compounds formed after the first discharge has a very high cyclability, as shown the low capacity loss <1% per cycle.     

Spectroscopic properties and conduction mechanism of KAl(SO4)2:xSm: A multifunctional materials for optical and electrochemical applications

Anhydrous α-alum materials doped with the trivalent samarium oxide Sm₂O₃ and denoted as KAl(SO₄)₂:xSm (x = 0; 0.5; 1; 1.5; 2; 2.5% mol.) are prepared by the solid-state reaction method at 350 °C. The resulting phases are crystallized in a simple hexagonal structure with space group P321. Powder X-ray diffraction (XRD), Infrared (IR), and Raman spectroscopies confirmed a high purity of phases with variation in lattice parameters according to the amount of doping.Optical measurements through absorption and fluorescence spectroscopies in the ultra-violet and visible regions prove the different electronic transitions between excited levels and ⁶H_5/2 ground state of Sm³⁺, the incorporation of samarium in the crystal structure, and suggest the quenching phenomenon.The materials presented in the study showed an ionic semiconductor behavior with an increase in their conductivity as a function of the doping level. A 1D conduction is made according to the Correlated Barrier Hopping CBH model by cations mobility in crystalline sites under the effect of thermal agitation in the [170–250 °C] region. KAl(SO₄)₂: xSm (x = 1.5% mol.) with its lower activation energy value, is suggested as a suitable cathode material for aluminum-based batteries.     

Study of IrxRu1−xO2 oxides as anodic electrocatalysts for solid polymer electrolyte water electrolysis

Electrocatalysts of the general formula Ir_xRu_1−xO₂ were prepared using Adams’ fusion method. The crystallite characterization was examined via XRD, and the electrochemical properties were examined via cyclic voltammetry (CV) in, linear sweep voltammetry (LSV) and chronopotentiometry measurements in 0.5 M H₂SO₄. The electrocatalysts were applied to a membrane electrode assembly (MEA) and studied in situ in an electrolysis cell through electrochemical impedance spectroscopy (EIS) and stationary current density–potential relations were investigated. The Ir_xRu_1−xO₂ (x = 0.2, 0.4, 0.6) compounds were found to be more active than pure IrO₂ and more stable than pure RuO₂. The most active electrocatalyst obtained had a composition of Ir_0.2Ru_0.8O₂. With an Ir_0.2Ru_0.8O₂ anode, a 28.4% Pt/C cathode and the total noble metal loading of 1.7 mg cm⁻², the potential of water electrolysis was 1.622 V at 1 A cm⁻² and 80 °C.