Hierarchical structured ZnFe<Subscript>2</Subscript>O<Subscript>4</Subscript>@RGO@TiO<Subscript>2</Subscript> composite as powerful visible light catalyst for degradation of fulvic acid

Hierarchical structured ZnFe₂O₄@reduced graphite oxide@TiO₂ (ZnFe₂O₄@RGO@TiO₂) nanocomposite was prepared by an electrostatic layer-by-layer route, which played a synthetic effect of Fenton oxidation of ZnFe₂O₄ and photocatalytic oxidation of TiO₂ to degrade fulvic acid (FA) solution under visible-light irradiation. In this method, RGO, as the middle layer, can effectively promote the photo-induced electron flow between the ZnFe₂O₄ and TiO₂ and further improve the efficiency of the photo-Fenton oxidation. The influencing factors on photo-Fenton oxidation, including solution pH, catalyst, and H₂O₂ dosage, have also been investigated. The results illustrated that the ternary composite presented the enhanced catalytic performance. Under visible light irradiation, the degradation efficiency of the sample on the FA solution can reach 95.4% within 3 h. In addition, the catalyst exhibited superior stability and reusability, and its degradation efficiency was still up to 90% after 5 cycles. Therefore, the composite will be a kind of efficient photocatalyst and had a promising application for visible-light driven destruction of organic pollutants.     

The formation and electrochemical property of lithium-excess cathode material Li<Subscript>1.2</Subscript>Ni<Subscript>0.13</Subscript>Co<Subscript>0.13</Subscript>Mn<Subscript>0.54</Subscript>O<Subscript>2</Subscript> with petal-like nanoplate microstructure

Lithium-excess oxide shows great potential for its high specific capacity of exceeding 280 mAh g^?1. However, the poor rate capability caused by the poor electrochemical kinetics condition as well as the structure instability block the way of its application. Here, we aimed to improve the kinetics circumstance for lithium ion transference through the material bulk by synthesizing lithium-excess oxide with high specific surface area. Petal-like nanoplates and nanoparticles with excellent electrochemical performance were obtained at different sintering temperatures and times by the electrospinning-sintering method, which facilitates the sufficient contact of electrode and electrolyte and helps to reduce the polarization during the electrochemical reaction process. Cyclic voltammetry tests verify that a portion of oxidized oxygen is reduced reversibly at 3.0 V and the reduction of oxygen contributes to the discharge capacity. Electrochemical impedance spectroscopy plots illustrate the ameliorative electrochemical kinetics is conductive to the oxidation of oxygen at 4.5 V.     

Pd/WO<Subscript>3</Subscript>/C nanocomposite with APTMS-functionalized tungsten oxide nanosheet for formic acid electrooxidation enhancement

A Pd/WO₃/C nanocomposite with 3-aminopropyltrimethoxysilane (APTMS)-functionalized tungsten oxide nanosheets (Pd/WO₃/C-APTMS) was synthesized and applied as the efficient anode catalyst for direct formic acid fuel cells (DFAFCs). The mechanism for synthesizing the nanocomposite is as follows: initially, [PdCl₄]^2? was assembled onto the tungsten oxide nanosheets modified with APTMS. Following this, Pd nanoparticles were reduced via traditional impregnation reduction of [PdCl₄]^2? with NaBH₄. The transmission electron microscope (TEM) images revealed that the Pd nanoparticles were uniformly dispersed on WO₃ nanosheets and were approximately 2.7 nm in size. The electrochemical test results showed that enhanced electrocatalytic activity for the formic acid oxidation reaction (FAOR) was obtained on the Pd/WO₃/C catalyst compared with Pd/C. The higher electrocatalytic activity might be attributed to the uniform distribution of Pd with smaller particles. Furthermore, it is likely that the improvement in catalytic stability for the Pd/WO₃/C catalyst is due to the hydrogen spillover effect of WO₃ particles. These results indicate that this novel Pd/WO₃/C-APTMS nanocomposite exhibits promising potential for use as an anode electrocatalyst in DFAFCs.     

Enhanced electrochemical properties and thermal stability of LiNi<Subscript>1/3</Subscript>Co<Subscript>1/3</Subscript>Mn<Subscript>1/3</Subscript>O<Subscript>2</Subscript> by surface modification with Eu<Subscript>2</Subscript>O<Subscript>3</Subscript>

Layered LiNi_1/3Co_1/3Mn_1/3O₂ cathode material is synthesized via a sol-gel method and subsequently surface-modified with Eu₂O₃ layer by a wet chemical process. The effect of Eu₂O₃ coating on the electrochemical performances and thermal stability of LiNi_1/3Co_1/3Mn_1/3O₂@Eu₂O₃ cells is investigated systematically by the charge/discharge testing, cyclic voltammograms, AC impedance spectroscopy, and DSC measurements, respectively. In comparison, the Eu₂O₃-coated sample demonstrates better electrochemical performances and thermal stability than that of the pristine one. After 100 cycles at 1C, the Eu₂O₃-coated LiNi_1/3Co_1/3Mn_1/3O₂ cathode demonstrates stable cyclability with capacity retention of 92.9 %, which is higher than that (75.5 %) of the pristine one in voltage range 3.0–4.6 V. Analysis from the electrochemical measurements reveals that the remarkably improved performances of the surface-modified composites are mainly ascribed to the presence of Eu₂O₃-coating layer, which could efficiently suppress the undesirable side reaction and increasing impedance, and enhance the structural stability of active material.     

Influences on oxidation voltage and holding time on poly(3-methylthiophene) film for electrochromic stability

In this study, we report the influences of oxidation potential and holding time on the electrochromic(EC) stability of poly(3-methylthiophene)(P3MT) film during the electrochemical reaction. The cycle stability and transmittance changes of the film were investigated by optimizing the oxidation potential, and its chemical compositions were measured by x-ray photoelectron spectra after multiple electrochemical cycles. High oxidation potentials can increase the P3MT film color contrast and decrease its cycle stability because of accelerating chemical decomposition. Moreover, the holding time with potential pulsing was analyzed by using the optical memory of P3MT at an optimized oxidation potential, which revealed the reduced voltage duration saved energy consumption by 11.6% and improved the EC cycle stability without changing in color contrast.     

A comparative study for the electrocatalytic oxidation of alcohol on Pt-Au nanoparticle-supported copolymer-grafted graphene oxide composite for fuel cell application

The platinum-gold bimetallic nanoparticles supported poly(cyclotriphosphazene-co-benzidine)-grafted graphene oxide (poly(CP-co-BZ)-g-GO) composite has been prepared for electrochemical performance studies. Cyclic voltammetry and chronoamperometric studies were carried out to check the electrochemical properties of Pt-Au/poly(CP-co-BZ)-g-GO and Pt/poly(CP-co-BZ)-g-GO catalysts for methanol, ethylene glycol and glycerol in alkaline medium. The morphology and crystalline structure of the prepared Pt-Au/poly(CP-co-BZ)-g-GO and Pt/poly(CP-co-BZ)-g-GO and catalysts have been characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy dispersive spectroscopy (EDS), X-ray diffraction (XRD) and fourier transform infrared spectroscopy (FT-IR). From the electrochemical results, it was concluded that Pt-Au/poly(CP-co-BZ)-g-GO catalyst shows higher catalytic activity and stability compared to Pt/poly(CP-co-BZ)-g-GO catalyst. The catalytic activity of Pt/poly(CP-co-BZ)-g-GO catalyst has been compared with Pt/poly(CP-co-BZ), Pt/GO and Pt/C catalysts. In addition, oxidation current of ethylene glycol is higher than the methanol and glycerol in alkaline medium on the prepared catalyst.     

Sono-photo-Fenton oxidation of bisphenol-A over a LaFeO3 perovskite catalyst

In this study, oxidation of bisphenol-A (IUPAC name – 2,2-(4,4-dihydroxyphenyl, BPA), which is an endocrine disrupting phenolic compound used in the polycarbonate plastic and epoxy resin industry, was investigated using sono-photo-Fenton process under visible light irradiation in the presence of an iron containing perovskite catalyst, LaFeO₃. The catalyst prepared by sol–gel method, calcined at 500 °C showed a catalytic activity in BPA oxidation using sono-photo-Fenton process with a degradation degree and a chemical oxygen demand (COD) reduction of 21.8% and 11.2%, respectively. Degradation of BPA was studied by using individual and combined advanced oxidation techniques including sonication, heterogeneous Fenton reaction and photo oxidation over this catalyst to understand the effect of each process on degradation of BPA. It was seen, the role of sonication was very important in hybrid sono-photo-Fenton process due to the pyrolysis and sonoluminescence effects caused by ultrasonic irradiation. The prepared LaFeO₃ perovskite catalyst was a good sonocatalyst rather than a photocatalyst. Sonication was not only the effective process to degrade BPA but also it was the cost effective process in terms of energy consumption. The studies show that the energy consumption is lower in the sono-Fenton process than those in the photo-Fenton and sono-photo- Fenton processes.     

Spectroelectrochemical cell for in situ studies of solid oxide fuel cells

Solid oxide fuel cells (SOFCs) are able to produce electricity and heat from hydrogen‐ or carbon‐containing fuels with high efficiencies and are considered important cornerstones for future sustainable energy systems. Performance, activation and degradation processes are crucial parameters to control before the technology can achieve breakthrough. They have been widely studied, predominately by electrochemical testing with subsequent micro‐structural analysis. In order to be able to develop better SOFCs, it is important to understand how the measured electrochemical performance depends on materials and structural properties, preferably at the atomic level. A characterization of these properties under operation is desired. As SOFCs operate at temperatures around 1073 K, this is a challenge. A spectroelectrochemical cell was designed that is able to study SOFCs at operating temperatures and in the presence of relevant gases. Simultaneous spectroscopic and electrochemical evaluation by using X‐ray absorption spectroscopy and electrochemical impedance spectroscopy is possible.     

The enhanced catalytic degradation of SiO<Subscript>2</Subscript>/Fe<Subscript>3</Subscript>O<Subscript>4</Subscript>/C@TiO<Subscript>2</Subscript> photo-Fenton system on p-nitrophenol

Heterogeneous photo-Fenton SiO₂/Fe₃O₄/C@TiO₂ (SFCT) catalyst with a core-multishell structure and a diameter of about 550 nm was successfully prepared and was characterized by scanning electron microscopy (SEM), TEM, XRD, Raman, and Fourier transform infrared (FT-IR). The results illustrated that anatase TiO₂ coexisted with rutile TiO₂, in which the anatase phase was the main crystal phase. In addition, the catalytic activity of SFCT catalyst had been evaluated in the catalytic degradation on p-nitrophenol (PNP). The influence factors on the PNP degradation, including SFCT component ratio (m _SFC/ m _TiO2), H₂O₂ dosage, solution pH, and PNP concentration, had been investigated. And the contrast experiments about the photo-Fenton catalytic mechanism revealed that the SFCT-2 catalyst possessed a superior activity in the neutral environment due to the optimal activity matching between Fe₃O₄ and TiO₂, and it exhibited the stable catalytic performance after five successive recycles. Therefore, the SFCT-2 catalyst had a promising application for the photo-Fenton degradation of organic contaminant.     

La<Subscript>9.33</Subscript>Si<Subscript>6</Subscript>O<Subscript>26</Subscript> electrolyte thin films for IT-SOFC application deposited by a HIPIMS/DC hybrid magnetron sputtering process

Apatite-type La_9.33Si₆O₂₆ thin films were elaborated by co-sputtering of two metallic La and Si targets powered, respectively, by high power impulse magnetron sputtering and direct current sources, in pure Ar atmosphere, followed by a subsequent high temperature oxidation treatment in air. The structural and chemical features of these films have been assessed by X-ray diffraction and scanning electron microscopy (SEM). The film with near lanthanum silicate La/Si atomic ratio deposited on a porous Ni-YSZ cermet substrates was initially amorphous. After thermal oxidation at 1,173 K in air, the coating crystallised under the expected apatite structure. SEM observation revealed that both film compactness and thickness increased after thermal oxidation. The conductivity evolution with temperature of the pure apatite-like lanthanum silicate coatings, as measured by complex impedance spectroscopy, showed that the activation energy of is quite low compared to the literature data.     

太阳能光催化制氢的科学机遇和挑战

面对人类对能源的需求持续增长,以及化石能源的日益枯竭和其带来的环境污染问题,太阳能成为主要的可再生清洁能源的来源。讨论了利用太阳能催化生氢或消耗二氧化碳,探索在半导体基光催化剂表面的光催化反应和光化学反应。半导体材料被认为是最有前景的光催化剂,其材料合成是发展先进催化剂的核心。减少电荷重新复合,是提高太阳能转化为化学能的关键,关系到太阳能的转换效率。研究结果发现了提高光催化制氢的关键因素,通过Pt-PdS/CdS催化体系使其量子效率提高到93%,提供了发展高效催化剂体系的方法。     

Preparation of highly dispersed Pt-SnOx nanoparticles supported on multi-walled carbon nanotubes for methanol oxidation

To maximize the utilization of catalysts and thereby reduce the high price, a new strategy was developed to prepare highly dispersed Pt-SnO_x nanoparticles supported on 8-Hydroxyquinoline (HQ) functionalized multi-walled carbon nanotubes (MWCNTs). HQ functionalized MWCNTs (HQ-MWCNTs) provide an ideal support for improving the utilization of platinum-based catalysts, and the introduction of SnO_x to the catalyst prevents the CO poisoning effectively. The as-prepared catalysts are characterized by Transmission electron microscopy (TEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and Raman spectroscopy. It is found that the HQ functionalization process preserves the integrity and electronic structure of MWCNTs, and the resulting Pt-SnO_x particles are well dispersed on the HQ-MWCNTs with an average diameter of ca. 2.2 nm. Based on the electrochemical properties characterized by cyclic voltammetry and chronoamperometry, the Pt-SnO_x/HQ-MWCNTs catalyst displays better electrocatalytic activity and stability for the methanol oxidation. It is worth mentioning that the forward peak current density of Pt-SnO_x/HQ-MWCNTs catalyst is ca. 1.9 times of that of JM commercial 20% Pt/C catalyst, which makes it the preferable catalyst for direct methanol fuel cells.     

Features of the formation of an oxide layer on the surface of amorphous Zr<Subscript>41.2</Subscript>Ti<Subscript>13.8</Subscript>Cu<Subscript>12.5</Subscript>Ni<Subscript>10.0</Subscript>Be<Subscript>22.5</Subscript> alloy

Field investigations were performed into the nature of oxidation of Zr_41.2Ti_13.8Cu_12.5Ni_10.0Be_22.5 alloy (Vitreloy-1), a new alloy highly promising for in -vessel mirrors of the ITER (International Thermonuclear Experimental Reactor). The main methods of investigation were X-ray photoelectron spectroscopy and multi-angle ellipsometry. The resistance of the optical properties of Vitreloy-1 against radiation impact was explained by the oxidation of the surface layer, based on the features of the diffusion process in amorphous alloys and of interaction between amorphous metal alloys with hydrogen.     

Vibrational modes of acid hydrogen in CsH<Subscript>5</Subscript>(PO<Subscript>4</Subscript>)<Subscript>2</Subscript> and NaH<Subscript>5</Subscript>P<Subscript>2</Subscript>O<Subscript>6</Subscript>: inelastic neutron scattering

The vibrational modes of hydrogen bonds in CsH₅(PO₄)₂ and NaH₅P₂O₆ compounds are analyzed via inelastic incoherent neutron scattering in a wide range of temperatures and Raman light scattering at room temperature. The energy ranges have been determined for the γ, jg, and ? bands of the vibrational modes of acid hydrogens of these compounds. The dependences of the energy on the length of hydrogen bonds in CsH₅(PO₄)₂ have been revealed.     

Ultrathin Fe‐N‐C Nanosheets Coordinated Fe‐Doped CoNi Alloy Nanoparticles for Electrochemical Water Splitting

The development of highly active and cost‐effective catalyst materials toward electrochemical water splitting is of great importance for converting and storing the intermittent solar energy in the form of hydrogen. Herein, for the first time, an ultrathin Fe and N‐co‐doped carbon nanosheet encapsulated Fe‐doped CoNi alloy nanoparticle (FeCoNi@FeNC) composite is obtained and applied as a bifunctional catalyst for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). This catalyst exhibits prominent catalytic performances for both HER and OER, which only requires overpotentials of 102 and 330 mV, respectively, to reach a current density of 10 mA cm^?2 in alkaline media. The high catalytic activity is intrinsically associated with the presence of Fe in both nanosheets and nanoparticles, which has triggered the occurrence of coordinative effects between Fe‐N‐C and FeCoNi that are beneficial for HER and OER, as revealed by electrochemical techniques. In an overall water splitting electrolyzer, FeCoNi@FeNC is employed as both the cathode and anode catalysts, achieving 12 mA cm^?2 at 1.63 V for a duration of more than 12 h.     

Quantum processes in 8-Oxo-Guanine-Ru(bipyridine)<Stack><Subscript>3</Subscript><Superscript>2+</Superscript></Stack> photosynthetic systems of artificial minimal cells

Density functional theory methods were used to investigate various self-assembled photoactive bioorganic systems of interest for artificial minimal cells. The cell systems studied are based on nucleotides or their compounds and consisted of up to 123 atoms (not including the associated water or methanol solvent shells) and are up to 2.5 nm in diameter. The electron correlation interactions responsible for the weak hydrogen and Van derWaals chemical bonds increase due to the addition of a polar solvent (water or methanol). The precursor fatty acid molecules of the system also play a critical role in the quantum mechanical interaction based self-assembly of the photosynthetic center and the functioning of the photosynthetic processes of the artificial minimal cells. The distances between the separated sensitizer, fatty acid precursor, and methanol molecules are comparable to Van derWaals and hydrogen bonding radii. As a result the associated electron correlation interactions compress the overall system, resulting in an even smaller gap between the highest occupied molecular orbital (HOMO), and lowest unoccupied molecular orbital (LUMO) electron energy levels and photoexcited electron tunnelling occurs from the sensitizer (either Ru(bpy)₃²⁺ or [Ru(bpy)2(4-Bu-4’-Me-2,2’-bpy)]²⁺+ derivatives) to the precursor fatty acid molecules (notation used: Me = methyl; Bu = butyl; bpy = bipyridine). The shift of the absorption spectrum to the red for the artificial protocell photosynthetic centers might be considered as the measure of the complexity of these systems.     

铁基触媒中碳化硼含量对含硼金刚石单晶表观活化能的影响

通过在铁基触媒中添加适量的碳化硼,制备出了具有不同硼含量的含硼金刚石单晶。利用差热分析仪,测量了含硼金刚石单晶的差热和热重。采用Kissinger方法,计算了含硼金刚石单晶在加热过程中发生氧化反应的表观活化能,对比分析掺硼量对含硼金刚石单晶热稳定性的影响。结果表明:差热和热重测量值与表观活化能计算值的变化规律基本一致;随着掺硼量的增加,含硼金刚石单晶的热稳定性先提高后降低,剧烈氧化时表观活化能随着掺硼量的增加而减小。     

绿色助溶剂三乙二醇在乙炔电化学氧化过程中的作用机制

建立在常温、常压条件下准确定量测定溶解乙炔含量的紫外-可见分光光度法,并对乙炔在丙酮、三乙二醇、N,N-二甲基甲酰胺和二甲基亚砜中的溶解特性进行系统考察;采用循环伏安法研究助溶剂丙酮、三乙二醇、N,N-二甲基甲酰胺和二甲基亚砜对乙炔电化学氧化过程的影响以及绿色溶剂TEG对该过程影响的作用机制。实验结果表明在常温、常压条件下,溶解乙炔的含量可采用紫外-可见分光光度法通过紫红色的乙炔铜进行准确测定,N,N-二甲基甲酰胺溶解乙炔的能力最强;在乙炔电化学氧化过程中,水分子和三乙二醇之间强烈的氢键作用是提高乙炔在Na₂SO₄溶液中溶解度的决定性因素;在含体积分数为9%TEG的0.5 mol·L-1 Na₂SO₄溶液中,乙炔电化学氧化过程的表观活化能为13.20 kJ·mol-1,属于受吸附控制的不可逆过程。该研究以期寻找一种乙炔的良好溶剂,为乙炔电化学氧化过程的研究、乙炔传感器(尤其是乙炔的电化学传感器)、绿色化学以及乙炔化工等的发展提供理论依据和实验指导。     

A lithium salt additive Li<Subscript>2</Subscript>ZrF<Subscript>6</Subscript> for enhancing the electrochemical performance of high-voltage LiNi<Subscript>0.5</Subscript>Mn<Subscript>1.5</Subscript>O<Subscript>4</Subscript> cathode

In this work, Li₂ZrF₆, a lithium salt additive, is reported to improve the interface stability of LiNi_0.5Mn_1.5O₄ (LNMO)/electrolyte interface under high voltage (4.9 V vs Li/Li⁺). Li₂ZrF₆ is an effective additive to serve as an in situ surface coating material for high-voltage LNMO half cells. A protective SEI layer is formed on the electrode surface due to the involvement of Li₂ZrF₆ during the formation of SEI layer. Charge/discharge tests show that 0.15 mol L^?1 Li₂ZrF₆ is the optimal concentration for the LiNi_0.5Mn_1.5O₄ electrode and it can improve the cycling performance and rate property of LNMO/Li half cells. The results obtained by electrochemical impedance spectroscopy (EIS), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and X-ray photoelectron spectroscopy (XPS) demonstrate that Li₂ZrF₆ can facilitate the formation of a thin, uniform, and stable solid electrolyte interface (SEI) layer. This layer inhibits the oxidation decomposition of the electrolyte and suppresses the dissolution of the cathode materials, resulting in improved electrochemical performances.     

Co<Subscript>3</Subscript>O<Subscript>4</Subscript>@MnO<Subscript>2</Subscript> core shell arrays on nickel foam with excellent electrochemical performance for aqueous asymmetric supercapacitor

At present, a lot of attention has been paid to the reasonable design and synthesis of materials with core shell structure for high-performance supercapacitors. Herein, the Co₃O₄@MnO₂ core shell arrays on nickel foam are successfully synthesized via a facile and effective hydrothermal method followed with annealing process. The sample was characterized by X-ray diffraction, scanning electron microscopy, and transmission electron microscopy. Electrochemical performance of the Co₃O₄@MnO₂ material was studied using cyclic voltammetry, charge/discharge cycling, and electrochemical impedance measurements in 6 mol L^?1 KOH aqueous electrolyte. The results indicated that the Co₃O₄@MnO₂ material presented excellent electrochemical performance in terms of specific capacitance, cyclic stability, and charge/discharge stability.