Surface reconstruction of Se-doped NiS_(2) enables high-efficiency oxygen evolution reaction

Surface reconstruction of electrocatalysts has been widely witnessed during the electrochemical processes.Here,NiS_(2),NiSe_(2), and Se doped NiS_(2)(Se-NiS_(2)) are fabricated for oxygen evolution reaction(OER) through a mild sulfuration and/or selenylation process of Ni(OH)_(2) supported on carbon cloth(CC).Through careful in-situ Raman spectroscopy and ex-situ X-ray photoelectron spectroscopy,surface reconstruction of NiS_(2),NiSe_(2),and Se-NiS_(2) during the OER process has been revealed.A potentialdependent study shows that Se-NiS_(2) undergoes surface evolution at lower potentials and requires the lowest potential for conversion to NiOOH as a highly OER-active species,accompanied by the leaching of SO_(4)^(2-) and SeO_(4)^(2-) that can again be adsorbed on the catalyst surface to enhance the catalytic activity.Density functional theory(DFT) calculations confirm that Se-NiS_(2) is more susceptible to surface oxidation through the OER process.Therefore,Se-NiS_(2) exhibits outstanding OER activity and stability in alkaline conditions,requiring an overpotential of 343 mV at a current density of 50 mA cm^(-2).A novel insight is provided by our work in understanding the surface reconstruction and electrocatalytic mechanism of Ni-based chalcogenides.

In-situ hydrothermal synthesized γ-Al_2O_3/O-g-C_3N_4 heterojunctions with enhanced visible-light photocatalytic activity in water splitting for hydrogen

In this work, γ-Al2O3and hydrogen peroxide treated g-C3N4(O-g-C3N4) were combined through a novel in-situ hydrothermal method to form heterojunction structured photocatalysts. These photocatalysts were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FT-IR), X-ray photoelectron spectroscopy (XPS), UV–vis diffuse reflectance spectroscopy and photoluminescence spectroscopy (PL). FT-IR results indicate that oxygen functional groups can be grafted on the surface of O-g-C3N4by hydrogen peroxide treatment. The visible light photocatalytic hydrogen evolution rate was investigated in 10 vol% TEOA aqueous solution. The optimal Al2O3mass content is set to be 20 wt% and the corresponding hydrogen evolution rate is 1288 µmol/h/g which is approximately 6, 3 folds that of pristine g-C3N4and O-g-C3N4respectively and 1.6 folds that of mechanical mixed composite with the same Al2O3mass content. The photocurrent density–time curves were carried out under visible light illumination for four on–off cycles. The electrochemical impedance spectroscopy (EIS) measurements verified the enhanced separation efficiency of electron–hole pairs. This work raised a new method to form the heterojunction structured photocatalysts and achieved a remarkable improvement of the photocatalytic activity in water splitting for hydrogen under visible light irradiation. © 2016

IN-SITU HVEM STUDY ON PHASE TRANSITION OF YBa_2Cu_3O_(7-x) SUPERCONDUCTING COMPOUND IN PROCESS OF HEATING

In-situ HVEM observation on phase transition of the YBa_2Cu_3O_(7-x) superconducting compound in pro- cess of heating was carried out,and high temperature X-ray diffraction analysis in air and X-ray diffraction phase analysis for the sample treated in vacuum condition were made.The results showed that the temperature of phase transition is related to oxygen content in the sample and in general,is 100℃ to 120℃ lower in vacu- um condition than in air.At 320℃ to 350℃ twin bands begin to disappear,and some Cu_2O are formed on the surface of the sample and transit from orthorhombic YBa_2Cu_3O_(7-x) to arthorhombic Y_2BaCuO_5 compound. This transition was completed at about 500℃.Above 900℃,this compound consists of the Y_2BaCuO_5, BaCuO_2,Y_2O_3 and some other minor compounds.No phase transition was observed during cooling the sample.

氧化钠对CaO-Al_(2)O_(3)-SiO_(2)三元系铝酸钙形成规律的影响(英文)

利用XRD、SEMEDS和DSCTG技术研究了添加Na2O的CaO-Al2O3-SiO2体系中铝酸钙的形成规律。结果表明,当Al2O3与SiO2的质量比为3.0、CaO与Al2O3的摩尔比为1.0时,在1350°C烧结后的熟料主要由12CaO·7Al2O3、2CaO·Al2O3·SiO2和2CaO·SiO2组成。熟料中12CaO·7Al2O3的含量随着Na2O的增加而增加,2CaO·Al2O3·SiO2的含量随着Na2O的增加而降低。Na2O在12CaO·7Al2O3中形成固溶体,增加了其单位晶胞体积。DSC分析表明,Na2O不仅促进了12CaO·7Al2O3的形成,而且使C12A7的形成温度降低了30°C。烧结熟料中的氧化铝溶出性能随着Na2O的增加而大幅度提高。

不同灌溉方式旱田土壤N_(2)O排放和氮素淋溶特征

通过野外原位监测试验,利用静态箱-气相色谱法、土壤溶液提取器分别对旱田土壤N_(2)O排放及氮素淋溶进行2018和2019年连续两年观测.试验设计为DCK(滴灌无肥)、DD(滴灌+N 500kg/hm^(2))、DG(滴灌+N 1000kg/hm^(2))、FCK(沟灌无肥)、FD(沟灌+N 500kg/hm^(2))、FG(沟灌+N 1000kg/hm^(2)).结果表明,不同施氮量、不同灌溉方式对N_(2)O排放和氮素淋溶量影响具有极显著差异(P<0.01).N_(2)O排放量随施氮量的增加而增加,滴灌与沟灌相比可有效降低N_(2)O排放,2018和2019年FCK、FD、FG的N_(2)O累积排放量分别为2,23.79,45.73kg/hm^(2)和2.08,6.23,13.93kg/hm^(2),而DCK、DD、DG分别降低了35%、80.9%、75.6%和26.7%、66.4%、21.5%.2018和2019年旱田土壤氮素淋溶量均表现为:滴灌<沟灌,80cm深度土壤溶液氮素淋溶量<40cm.2018和2019年相同施氮量下滴灌与沟灌相比,在40cm和80cm分别能减少氮素淋溶量36.95%~63.10%和54.93%~87.92%.主成分分析结果表明,影响N_(2)O排放的主要环境因子为土壤NO_(3-)-N含量和降水频率,相关系数分别为0.689、0.596;影响氮素淋溶量的主要环境因子为降水频率和灌水频率,相关系数分别为0.697和-0.729.滴灌可有效减少N_(2)O排放和氮素淋溶量,在提高肥料利用率的同时可减轻环境污染.

钛石膏-H_(2)SO_(4)-H_(2)O体系中石膏-硬石膏的相变规律

本文研究了在常压下钛石膏-H_(2)SO_(4)-H_(2)O体系中石膏相向硬石膏相的转化,探索了反应时间、硫酸浓度和温度对石膏-硬石膏转化的影响。结果表明:提高反应温度、增大硫酸浓度和增加反应时间都有利于石膏向硬石膏转化;当石膏转化为硬石膏后,延长反应时间硬石膏不再发生转变;在温度为70℃和80℃时,体系中石膏与硬石膏共存,二者的微观形貌差异明显,石膏呈片状,硬石膏呈长方板状;当温度升温至90℃以上时,石膏完全转变为硬石膏,其微观形貌为长方板状;常压下,在50~100℃内,在钛石膏-H_(2)SO_(4)-H_(2)O体系中发生的石膏-硬石膏的相变是石膏直接脱水形成硬石膏,没有中间产物形成。

CO预处理对CuO/γ-Al_2O_3催化剂性能的影响

采用XRD，TPR，CO吸附in—situ IR，CO氧化反应等对CuO／y—Al2O3催化剂经CO处理前后的结构、组成和催化性能进行了研究。结果表明，经CO在250℃下处理1h后CuO／y—Al2O3，催化剂中出现了分散态Cu^＋物种，该物种的产生使催化剂的活性明显提高。

Studies on the Structure and Properties of Multiphase Al_2O_3 Abrasion-resistant Ceramics

The Al2O3 abrasion-resistant ceramics is successfully prepared by using waste aluminum sludge as the main raw material with the addition of a little clay, talc and barium carbonate. The crystal structure and microstructure of ceramic are characterized by means of XRD, SEM, etc., and the physical and mechanical properties are also tested. The results show that besides the phase of corundum, a little mullite, Mg-Al spinel and hyalophane phases also exist in the product. These phases are produced via reaction in-situ, which can inhibit the overgrowth of Al2O3 grain in grain boundary, and improve the integral property of the material.

Fabrication of Fine-Grained Si_3N_4-Si_2N_2O Composites by Sintering Amorphous Nano-sized Silicon Nitride Powders

Si3N4-Si2N2O composites were fabricated with amorphous nano-sized silicon nitride powders by the liquid phase sintering （ LPS ）. The Si2 N2O phase was generated by an in-situ reaction 2 Si3 N4 （ s ） ＋ 1.5 02 （ g ） = 3 Si2 N2O （ s ） ＋ N2 （ g ） . The content of Si2 N2 O phase up to 60% in the volume was obtained at a sintering temperature of 1 650℃ and reduced when the sintering temperature increased or decreased, indicating the reaction is reversible. The mass loss, relative density and average grain size increased with increasing the sintering temperature. The average grain size was less than 500 nm when the sintering temperature was below 1 700 ℃. The sintering procedure contains a complex crystallization and a phase transition ： amorphous silicon nitride→equiaxial α- Si3 N4→ equiaxial β- Si3 N4→ rod- like Si2 N2O→ needle- like β- Si3N4 . Small round-shaped β→ Si3 N4 particles were entrapped in the Si2 N2O grains and a high density of staking faults was situated in the middle of Si2 N2O grains at a sintering temperature of 1 650 ℃. The toughness inereased from 3.5 MPa·m^1/2 at 1 600 ℃ to 7.2 MPa· m^1/2 at 1 800 ℃ . The hardness was as high as 21.5 GPa （Vickers） at 1 600 ℃ .

(NH_(4))_(2)SO_(4)-NH_(3)-H_(2)O体系浸出高碱性脉石低品位氧化铜矿

以高碱性脉石低品位氧化铜矿为研究对象,针对该矿样钙镁含量高的特点,采用氨水-硫酸铵浸出体系进行了常温常压浸出实验.针对该矿样的主要含铜矿物孔雀石(Cu_(2)(OH)_(2)CO_(3)),基于质量和电荷的双守恒的条件下构建的浸出体系中建立Cu_(2)(OH)_(2)CO_(3)-(NH_(4))_(2)SO_(4)-NH_(3)-H_(2)O的热力学模型,采用Matlab的拟合功能与diff和solve函数算出不同硫酸铵浓度时氨浸出孔雀石的最佳氨浓度和总铜离子浓度.实验考察了浸出氨水浓度、氨铵比、液固比对铜浸出率的影响.实验结果表明,高碱性脉石氧化铜矿石适宜浸出条件为氨水浓度1.2 mol/L,氨铵比2∶1,液固比3∶1,该条件下铜浸出率较高,达到约70%.实验结果与热力学计算结果基本吻合.

In situ prepared Al-Si alloy matrix composites reinforced by γ-Al_2O_3p

A γ-Al2O3 particles reinforced Al-Si alloy matrix composite was fabricated by adding NH4Al（SO4）2 to molten aluminum alloy. TEM observation shows that in-situ γ-Al2O3 particles are generally spherical and uniformly distributed in the matrix. The results of dry sliding wear tests show that the wear resistance of the composites increases with increasing mass fraction, and the volume loss is considerably lesser than that of the matrix and is lesser than that of the composites by adding γ-Al2O3 particles directly.

Synthesis and electrochemical properties of LiMn_2O_4/Li_4Ti_5O_(12) composite

LiMn2O4/Li4Ti5O12 composite was synthesized by in-situ composite technique using LiMn2O4,lithium acetate,tetrabutyl titanate as starting materials and characterized by various electrochemical methods in combination with X-ray diffractometry(XRD), infrared(IR)spectroscopy and scanning electron microscopy(SEM).The results show that Li4Ti5O12 is coated on the surface of crystalline LiMn2O4 to form LiMn2O4/Li4Ti5O12 composite.The structure of LiMn2O4 does not change due to the introduction of Li4Ti5O12.By being coated with Li4Ti5O12,the rate capability and high temperature cyclability of LiMn2O4 is improved greatly.At room temperature,the discharge capacity of LiMn2O4/Li4Ti5O12 composite is more than 108.4 mA·h/g and the capacity loss per cycle is only 0.053%after 20 cycles at 2.0C.While at 55℃,the discharge capacity of LiMn2O4/Li4Ti5O12 composite is more than 109.9 mA·h/g and the capacity loss per cycle is only 0.036%after 60 cycles at 1.0C.

Recovery of valuable elements from spent YBa_2Cu_3O_(7-x)/Agcomposite superconductor bulks

Silver as a highly conductive metal is usually doped in YBa2Cu3O7-x superconductor bulks to improve critical current density of YBa2Cu3O7-x superconductor.The valuable metal elements silver,yttrium,barium and copper in waste YBa2Cu3O7-x/Ag composite superconductor bulks were recovered,respectively.Silver was recovered with process at first,the waste was dissolved by nitric acid and silver chloride was precipitated by adding chloride acid,then silver pig was obtained by melting silver chloride together with sodium carbonate at 1 000℃.The effective factors on recovery ratio and purity of silver were studied.The chemical analysis proves that the purity of silver ingot is 95.86%.The recovery ratio of silver is calculated to be 92.56%.The loss of silver may be due to the loss of silver chloride during filtering and the volatilization of silver when silver chloride and sodium carbonate are smelted at high temperature.For other three metal elements,Y3 +,Ba 2+and Cu 2+,in the surplus waste liquid after recovering silver, they were separated with the sequence of barium,copper and then yttrium step by step.First,sulfate acid was used to precipitate barium sulfate.Then,sodium sulfide was added to the surplus solution so that copper could be separated as copper sulfide.During this separation procedure,it was important to control the pH value to be 1-2.After that,oxalic acid was added into the surplus solution to obtain yttrium oxalate.Finally,yttrium oxide was formed by burning yttrium oxalate.The XRD results indicate that the final products are all single-phase compounds as BaSO4,CuS and Y2O3,respectively.

Electrochemical and structural evolution of structured V_(2)O_(5) microspheres during Li-ion intercalation

With the development of stable alkali metal anodes,V_(2)O_(5) is gaining traction as a cathode material due to its high theoretical capacity and the ability to intercalate Li,Na and K ions.Herein,we report a method for synthesizing structured orthorhombic V_(2)O_(5) microspheres and investigate Li intercalation/deintercalation into this material.For industry adoption,the electrochemical behavior of V_(2)O_(5) as well as structural and phase transformation attributing to Li intercalation reaction must be further investigated.Our synthesized V_(2)O_(5) microspheres consisted of small primary particles that were strongly joined together and exhibited good cycle stability and rate capability,triggered by reversible volume change and rapid Li ion diffusion.In addition,the reversibility of phase transformation(a,e,d,c and xLixV_(2)O_(5))and valence state evolution(5+,4+,and 3.5+)during intercalation/de-intercalation were studied via in-situ X-ray powder diffraction and X-ray absorption near edge structure analyses.

Construction of N,O co-doped carbon anchored with Co nanoparticles as efficient catalyst for furfural hydrodeoxygenation in ethanol

Hydrodeoxygenation of furfural(FF)into 2-methylfuran(MF)is a significant biomass utilization route.However,designing efficient and stable non-noble metal catalyst is still a huge challenge.Herein,we reported the N,O co-doped carbon anchored with Co nanoparticles(Co-SFB)synthesized by employing the organic ligands with the target heteroatoms.Raman,electron paramagnetic resonance(EPR),electrochemical impedance spectroscopy(EIS),and X-ray photoelectron spectroscopy(XPS)characterizations showed that the co-doping of N and O heteroatoms in the carbon support endows Co-SFB with enriched lone pair electrons,fast electron transfer ability,and strong metal-support interaction.These electronic properties resulted in strong FF adsorption as well as lower apparent reaction activation energy.At last,the obtained N,O co-doped Co/C catalyst showed excellent catalytic activity(nearly 100 mol%FF conversion and 94.6 mol%MF yield)and stability for in-situ dehydrogenation of FF into MF.This N,O co-doping strategy for the synthesis of highly efficient catalytic materials with controllable electronic state will provide an excellent opportunity to better understand the structure-function relationship.

Nitrogen cycling and environmental impacts in upland agricultural soils in North China： A review

The upland agricultural soils in North China are distributed north of a line between the Kunlun Mountains, the Qinling Mountains and the Huaihe River. They occur in arid, semi-arid and semi-humid regions and crop production often depends on rain-fed or irrigation to supplement rainfall. This paper summarizes the characteristics of gross nitrogen（N） transformation, the fate of N fertilizer and soil N as well as the N loss pathway, and makes suggestions for proper N management in the region. The soils of the region are characterized by strong N mineralization and nitrification, and weak immobilization and denitrification ability, which lead to the production and accumulation of nitrate in the soil profile. Large amounts of accumulated nitrate have been observed in the vadose-zone in soils due to excess N fertilization in the past three decades, and this nitrate is subject to occasional leaching which leads to groundwater nitrate contamination. Under farmer＇s conventional high N fertilization practice in the winter wheat-summer maize rotation system（N application rate was approximately 600 kg ha–1 yr–1）, crop N uptake, soil residual N, NH_3 volatilization, NO_3~– leaching, and denitrification loss accounted for around 27, 30, 23, 18 and 2% of the applied fertilizer N, respectively. NH_3 volatilization and NO_3~– leaching were the most important N loss pathways while soil residual N was an important fate of N fertilizer for replenishing soil N depletion from crop production. The upland agricultural soils in North China are a large source of N_2O and total emissions in this region make up a large proportion（approximately 54%） of Chinese cropland N_2O emissions. The “non-coupled strong ammonia oxidation” process is an important mechanism of N_2O production. Slowing down ammonia oxidation after ammonium-N fertilizer or urea application and avoiding transient high soil NH4＋ concentrations are key measures for reducing N_2O emissions in this region. Further N management should aim to minimize N losses from crop and livestock production, and increase the recycling of manure and straw back to cropland. We also recommend adoption of the 4 R（Right soure, Right rate, Right time, Right place） fertilization techniques to realize proper N fertilizer management, and improving application methods or modifying fertilizer types to reduce NH_3 volatilization, improving water management to reduce NO_3~– leaching, and controlling the strong ammonia oxidation process to abate N_2O emission. Future research should focus on the study of the trade-off effects among different N loss pathways under different N application methods or fertilizer products.

A new process of extracting vanadium from stone coal

A new process of extracting vanadium from the stone coal vanadium ore in Fangshankou, Dtmhuang area of Gansu Province, China was introduced. Various leaching experiments were carried out, and the results show that the vanadium ore in Fangshankou is difficult to process due to its high consumption of acid and the high leaching rate of impurities. However, the leaching rate can be up to 80% and the content of V2O5 in the residue can be between 0.22%-0.25% in the process of ore fme grinding→oxidation roasting→mixing and ripening→aqueous leaching→P2O4 solvent extraction→sulfuric acid stripping→oxidation and precipitation→decomposition by heat. Also, the quality of flaky V205 produced by this process can meet the requirements of GB3283--87. The total leaching rate of vanadium is 70%. Also, three types of wastes are easy to treat. The vanadium extraction process is better in relation to the aspect of environmental protection than the sodium method.

In-situ growth and photoluminescence of β-Ga_2O_3 cone-like nanowires on the surface of Ga substrates

β-Ga2O3 cone-like nanowires have been in-situ grown on the surface of gallium grains and films by heating gallium substrates at 750-1000℃ for 2h in air.The controllable synthesis of β-Ga2O3 nano-wires with different diameters and lengths was achieved by adjusting the heating temperature and time.The as-synthesized products were characterized by means of X-ray diffraction,scanning electron mi-croscopy and transmission electron microscopy.The results showed that the β-Ga2O3 nanowires are single crystalline with a monoclinic structure and have a controllable diameter and length in the range of 30-100nm and 0.5-1.5μm,respectively.A possible mechanism was also proposed to account for the formation of β-Ga2O3 cone-like nanowires.Photoluminescence spectra of the β-Ga2O3 nanowires obtained at different temperatures were measured at room temperature,and a strong blue photolumi-nescence with peaks at 430 and 460nm and a weak red photoluminescence with peak at 713nm were observed.The blue light emission intensity decreases with increasing the reaction temperature,how-ever,the red light emission intensity hardly changes.The blue and red light emissions originate from the recombination of an electron on an oxygen vacancy with a hole on a gallium-oxygen vacancy pair and the nitrogen dopants,etc.,respectively.

In-situ growth of V2O5 flower-like structures on ceramic tubes and their trimethylamine sensing properties

V2O5 flower-like structures assembled by thin nanosheets were in-situ growth on ceramic tubes by hydrothermal process.The structural characterization indicates that V2O5 flower-like structures is orthogonal diamond phase,which entirely covered on the surface of ceramic tubes.TMA sensing measured results revealed that the sensor based on V2O5 flower-like structures exhibited fast reversible and response,good selectivity to TMA and good stability at 200℃.The good sensing performance may be ascribed to flower-like structure s and directly growth sensing film on the ceramic tube without structure damage.Our works give a simple in-situ growth flower-like structures route on sensing device,which exhibits potential application for detecting trace amounts of TMA gas.

废旧磷酸铁锂电池高值回收制备磷酸铁锂材料

针对传统湿法冶金回收废旧磷酸铁锂电池存在含磷废水排放量大、产品附加值低等问题,提出一种还原酸浸-沉淀-固相再生回收废旧磷酸铁锂正极材料的新方法。区别于传统氧化酸浸,本研究在浸出过程中加入有机还原剂,将铁元素以Fe^(2+)的形式浸出到溶液中;然后,通过控制pH值制备Fe_(3)(PO_(4))_(2)·8H_(2)O,以此作为再生LiFePO_(4)正极材料的前驱体,避免了后续混锂烧结过程中Fe^(3+)还原不彻底、再生磷酸铁锂纯度低等问题。结果表明:通过控制浸出条件,Li^(+)和Fe^(2+)的浸出率分别达到98.15%和98.10%。利用氨水调控浸出液pH值,沉淀出形貌为一次片状簇拥成团状结构的Fe_(3)(PO_(4))_(2)·8H_(2)O前驱体;最后,将Fe_(3)(PO_(4))_(2)·8H_(2)O与Li_(3)PO_(4)混合在真空管式炉中烧结再生LiFePO_(4)正极材料。电化学测试结果表明:再生的LiFePO_(4)正极材料在0.1C下的首次放电比容量为141.0 mA·h/g,1C循环200次后容量保持率为96.9%,表现出较为优异的电化学性能。