Mitigation of N_(2)O emissions in water-saving paddy fields:Evaluating organic fertilizer substitution and microbial mechanisms

Water-saving irrigation strategies can successfully alleviate methane emissions from rice fields,but significantly stimulate nitrous oxide(N_(2)O)emissions because of variations in soil oxygen level and redox potential.However,the relationship linking soil N_(2)O emissions to nitrogen functional genes during various fertilization treatments in water-saving paddy fields has rarely been investigated.Furthermore,the mitigation potential of organic fertilizer substitution on N_(2)O emissions and the microbial mechanism in rice fields must be further elucidated.Our study examined how soil N_(2)O emissions were affected by related functional microorganisms(ammonia-oxidizing archaea(AOA),ammonia-oxidizing bacteria(AOB),nirS,nirK and nosZ)to various fertilization treatments in a rice field in southeast China over two years.In this study,three fertilization regimes were applied to rice cultivation:a no nitrogen(N)(Control),an inorganic N(Ni),and an inorganic N with partial N substitution with organic manure(N_(i)+N_(o)).Over two rice-growing seasons,cumulative N_(2)O emissions averaged 0.47,4.62 and 4.08 kg ha^(−1)for the Control,Ni and N_(i)+N_(o)treatments,respectively.In comparison to the Ni treatment,the N_(i)+N_(o)fertilization regime considerably reduced soil N_(2)O emissions by 11.6%while maintaining rice yield,with a lower N_(2)O emission factor(EF)from fertilizer N of 0.95%.Nitrogen fertilization considerably raised the AOB,nirS,nirK and nosZ gene abundances,in comparison to the Control treatment.Moreover,the substitution of organic manure for inorganic N fertilizer significantly decreased AOB and nirS gene abundances and increased nosZ gene abundance.The AOB responded to N fertilization more sensitively than the AOA.Total N_(2)O emissions significantly correlated positively with AOB and nirS gene abundances while having a negative correlation with nosZ gene abundance and the nosZ/nirS ratio across N-fertilized plots.In summary,we conclude that organic manure substitution for inorganic N fertilizer decreased soil N_(2)O emissions primarily by changing the soil NO_(3)^(−)-N,pH and DOC levels,thus inhibiting the activities of ammonia oxidation in nitrification and nitrite reduction in denitrification,and strengthening N_(2)O reduction in denitrification from water-saving rice paddies.

Atomic Ni directional-substitution on ZnIn_(2)S_(4) nanosheet to achieve the equilibrium of elevated redox capacity and efficient carrier-kinetics performance in photocatalysis

It is a challenge to coordinate carrier-kinetics performance and the redox capacity of photogenerated charges synchronously at the atomic level for boosting photocatalytic activity.Herein,the atomic Ni was introduced into the lattice of hexagonal ZnIn_(2)S_(4) nanosheets(Ni/ZnIn_(2)S_(4))via directionalsubstituting Zn atom with the facile hydrothermal method.The electronic structure calculations indicate that the introduction of Ni atom effectively extracts more electrons and acts as active site for subsequent reduction reaction.Besides the optimized light absorption range,the elevation of Efand ECBendows Ni/ZnIn_(2)S_(4) photocatalyst with the increased electron concentration and the enhanced reduction ability for surface reaction.Moreover,ultrafast transient absorption spectroscopy,as well as a series of electrochemical tests,demonstrates that Ni/ZnIn_(2)S_(4) possesses 2.15 times longer lifetime of the excited charge carriers and an order of magnitude increase for carrier mobility and separation efficiency compared with pristine ZnIn_(2)S_(4).These efficient kinetics performances of charge carriers and enhanced redox capacity synergistically boost photocatalytic activity,in which a 3-times higher conversion efficiency of nitrobenzene reduction was achieved upon Ni/ZnIn_(2)S_(4).Our study not only provides in-depth insights into the effect of atomic directional-substitution on the kinetic behavior of photogenerated charges,but also opens an avenue to the synchronous optimization of redox capacity and carrier-kinetics performance for efficient solar energy conversion.

真空紫外协同Co^(2+)催化过硫酸氢钾降解罗丹明B

有机染料具有毒性强、色度高、不易降解等特性,为了高效去除有机染料,实验以真空紫外(VUV)为光源,研究了VUV协同Co^(2+)催化过硫酸氢钾(PMS)降解典型有机染料罗丹明B(RhB)的反应机制和转化途径.结果表明:①在RhB初始浓度为80 mg/L,Co^(2+)和PMS投加量分别为15μmol/L、0.5 mmol/L的条件下,VUV/Co^(2+)/PMS体系反应10 min,RhB去除率可达99.1%.VUV/Co^(2+)/PMS体系对RhB降解遵循一级动力学规律,反应速率常数(k)随初始质量浓度的增加而减小.②溶液初始pH对反应速率有较大的影响,随着pH减小,反应速率也同时减小.投加量为30 mmol/L的HCO_(3)^(−)、Cl^(−)均表现出显著的抑制作用,相较于对照组,RhB去除率由99.1%分别降至66.0%、84.2%,而NO_(3)^(−)和SO_(4)^(2−)抑制作用不显著;印染助剂柠檬酸钠也会显著抑制RhB降解.③自由基捕获实验和电子顺磁共振(EPR)测试结果表明,VUV/Co^(2+)/PMS体系中存在的氧化物种包括硫酸根自由基(SO_(4)^(−)·)、羟基自由基(·OH)、单线态氧(1O2).④根据紫外可见吸收光谱和质谱结果,初步推断RhB分子降解主要通过活性氧(ROS)攻击造成共轭结构破坏和N-位脱乙基等作用.另外,对总有机碳(TOC)进行测试,30 min时RhB矿化度可达到43.8%.研究显示,VUV/Co^(2+)/PMS体系能够有效去除RhB.

聚丙烯酸钠配合-超滤工艺分离电池废水中Mn^(2+)和Co^(2+)的试验

采用聚丙烯酸钠(PAAS)和聚醚砜(PES)中空纤维超滤(UF)膜,研究配合-超滤工艺对Mn^(2+)和Co^(2+)的截留效果、分离效果以及配合竞争效应。单金属离子试验结果表明:随着m(P)/m(M)(聚合物/金属离子质量比)、pH增加,Mn^(2+)和Co^(2+)的截留率增大。随温度增大,Mn^(2+)和Co^(2+)的截留率先增加后减小,Mn^(2+)、Co^(2+)的截留率分别在20、25℃时达到最大。pH值=5、m(P)/m(M)=4、温度为20℃为最佳操作条件,分离率最大(64.70%),配合竞争效应最强。NaCl减弱了金属离子的竞争配合能力,不利于Mn^(2+)和Co^(2+)的分离。混合金属离子试验的最佳操作条件下分离率为57.41%。红外数据显示,Mn^(2+)和Co^(2+)均与PAAS配合,由于离子水化热以及电负性的不同,Mn^(2+)和Co^(2+)与PAAS配合亲和力不同,在相同的溶液环境下,Mn^(2+)优先与PAAS配合。

Effects of sodium substitution on properties of LiMn_2O_4 cathode for lithium ion batteries

Na-doped Li1.05Mn2O4 cathodes were synthesized using a sol-gel process.The samples were characterized by X-ray diffractometry(XRD),cyclic voltammetry(CV),electrochemical impedance spectroscopy(EIS)and charge-discharge measurements. The results show that all the samples exhibit the same cubic spinel phase structure without impurity.The lattice constant and unit cell volume decrease with increasing the sodium dopant amount.As the molar ratio of sodium to manganese(x=n(Na)/n(Mn))increases from 0 to 0.03,the initial discharge capacity of the Li1.05Mn2O4 cathodes decreases from 119.2 to 107.9 mA·h/g,and the discharge capability at large current rate and the storage performance decline dramatically,while cycling performance at room temperature and 55℃are improved.The CV and EIS studies indicate that reversibility of Li1.05Mn2O4 cathodes decreases and the electrochemical impedance increases with increasing the sodium dopant amount.

A flexible design strategy to modify Ti3C2Tx MXene surface terminations via nucleophilic substitution for long-life Li-S batteries

MXene-based materials have gained considerable attention for lithium-sulfur(Li-S)batteries cathode materials due to their superior electric conductivity and high affinitive to polysulfides.However,there are still challenges in modifying the surface functional groups of MXene to further improve the electrochemical performance and increase the structure variety for MXene-based sulfur host.Herein,we report an efficient and flexible nucleophilic substitution(S_(N))strategy to modify the Ti_(3)C_(2)T_(x) surface terminations and purposefully designed Magnolol-modified Ti_(3)C_(2)T_(x)(M-Ti_(3)C_(2)T_(x))as powerful cathode host materials.Benefiting from more C-Ti-O bonds forming and diallyl groups terminations reducing after the dehalogenation and nucleophilic addition reactions,the given M-Ti_(3)C_(2)T_(x) electrode could effectively suppress the lithium polysulfides shuttling via chemisorption and C—S covalent bond formation.Besides,the Magnolol-modified Ti_(3)C_(2)T_(x) significantly accelerates polysulfide redox reaction and reduces the activation energy of Li_(2) S decomposition.As a result,the as-prepared M-Ti_(3)C_(2)T_(x) electrode displays an excellent rate capability and a high reversible capacity of 7.68 mAh cm^(-2)even under 7.2 mg cm^(-2)S-loaded with a low decay rate of 0.07%(from 2 nd cycle).This flexible surface-modified strategy for MXene terminations is expected to be extended to other diverse MXene applications.

Effect of erbium substitution on thermoelectric properties of complex oxide Ca_3Co_2O_6 at high temperatures

Polycrystalline particles of Ca3-xErxCo2O6 （x=0.0, 0.15, 0.3, 0.45 and 0.6） were synthesized using sol-gel method combined with Low Temperature Sintering procedure （LTS） to evaluate the effect of Er substitution on the thermoelectric properties of Ca3Co2O6. The crystal structure and microstructure were investigated using X-ray diffraction, infrared spectroscopy and scanning electron microscope. The electrical conductivity and Seebeck coefficient of the complex oxides were measured from 300 to 1073 K. The results showed that all the sampies were p-type semiconductors. The electrical conductivity increased with the increase in temperature. Er substitutions at Ca site affected carrier concentrations and carder mobility, resulting an increase in Seebeck coefficient and decrease in electrical conductivity. The power factor of Ca2.85Er0.15Co2O6 reached 10.66 μw/mK^2 at 1073 K.

Surface defect ordered Cu_(2)ZnSn(S,Se)_(4) solar cells with efficiency over 12% via manipulating local substitution

The environmentally friendly Cu_(2)ZnSn(S,Se)_(4)(CZTSSe) compounds are promising direct bandgap materials for application in thin film solar cells, but the spontaneous surface defects disordering would lead to large open-circuit voltage deficit(V_(oc,deficit)) and significantly limit kesterite photovoltaics performance,primarily arising from the generated more recombination centers and insufficient p to n conversion at p-n junction. Herein, we establish a surface defects ordering structure in CZTSSe system via local substitution of Cu by Ag to suppress disordered Cu_(Zn) defects and generate benign n-type Zn_(Ag) donors. Taking advantage of the decreased annealing temperature of Ag F post deposition treatment(PDT), the high concentration of Ag incorporated into surface absorber facilitates the formation of surface ordered defect environment similar to that of efficient CIGS PV. The manipulation of highly doped surface structure could effectively reduce recombination centers, increase depletion region width and enlarge the band bending near p-n junction. As a result, the Ag F-PDT device finally achieves maximum efficiency of 12.34% with enhanced V_(oc) of 0.496 V. These results offer a new solution route in surface defects and energy-level engineering, and open the way to build up high quality p-n junction for future development of kesterite technology.

微量Co^(2+)-Si^(4+)取代对多晶石榴石铁氧体材料旋矩磁性能的影响

采用传统陶瓷工艺制备了多晶石榴石铁氧体,研究了微量Co^(2+)-Si^(4+)联合取代对GdCaSnV-YIG、GdCaZrV-YIG、GdCaInV-YIG和GdAl-YIG材料旋矩磁性能的影响。结果表明,Co^(2+)-Si^(4+)联合取代GdAl-YIG可使其矫顽力显著增高,而Co^(2+)-Si^(4+)取代GdCaSnV-YIG、GdCaZrV-YIG和GdCaInV-YIG,可调节其矫顽力和剩磁比。当Co^(2+)-Si^(4+)取代量为0.015时得到GdCaSnV-YIG的矫顽力为0.17 Oe,取代量为0.025时得到GdCaZrV-YIG的矫顽力为0.23 Oe,取代量大于等于0.035时三者的剩磁比均能达到0.79或以上。

In situ Raman spectroscopy reveals the mechanism of titanium substitution in P2–Na_(2/3)Ni_(1/3)Mn_(2/3)O_(2): Cathode materials for sodium batteries

Layered P2–Na_(2/3)Ni_(1/3)Mn_(2/3)O_2 is a promising cathode material. It exhibits a high capacity and suitable operating voltage and undergoes a phase transition from P2 to O2 during charge/discharge.Researchers have used Ti substitution to improve the cathode, yet the chemical principles that underpin elemental substitution and functional improvement remain unclear. To clarify these principles, we used in situ Raman spectroscopy to monitor chemical changes in P2–Na2/3 Ni1/3 Mn1/3 Ti1/3 O2 and P2–Na_(2/3)Ni_(1/3)Mn_(2/3)O_2 during charge/discharge. Based on the change in the A_(1g) and E_g peaks during charge/discharge, we concluded that Ti substitution compressed the transition metal layer and expanded the planar oxygen layer in the unit cell. Titanium stabilized the P2 phase structure, which improved the cycling stability of P2–NaNMT. Our results provide clear theoretical support for future research on modifying electrodes by elemental substitution.

Precisely tuning Ge substitution for efficient solution-processed Cu_2ZnSn(S,Se)_4 solar cells

The kesterite Cu2ZnSn（S,Se）4 （CZTSSe） solar cells have yielded a prospective conversion efficiency among all thin- film photovoltaic technology. However, its further development is still hindered by the lower open-circuit voltage （Voc）, and the non-ideal bandgap of the absorber is an important factor affecting this issue. The substitution of Sn with Ge provides a unique ability to engineer the bandgap of the absorber film. Herein, a simple precursor solution approach was successfully developed to fabricate Cu2Zn（SnyGel_y）（SxSe~ x）4 （CZTGSSe） solar cells. By precisely adjusting the Ge content in a small range, the Voc and Jsc are enhanced simultaneously. Benefitting from the optimized bandgap and the maintained spike structure and light absorption, the 10% Ge/（Ge＋Sn） content device with a bandgap of approximately 1.1 eV yields the highest efficiency of 9.36%. This further indicates that a precisely controlled Ge content could further improve the cell performance for efficient CZTGSSe solar cells.

Assessment of Genetic Relationship and Application of Computational Algorithm to Assess Functionality of Non-Synonymous Substitutions in DQA2 Gene of Cattle, Sheep and Goats

The major histocompatibility complex (MHC) is a fundamental part of the immune system in nearly all vertebrates. DQA2 is a member of the MHC complex and an important candidate gene involved in susceptibility/resistance to various diseases. Therefore, the present study aimed at investigating computationally molecular genetic variation of DQA2 gene of cattle, sheep and goats especially on its evolution and differentiation within and among species as well as the attendant effects of the polymorphism on the function of DQA2 gene. A total of thirty three DQA2 nucleotide sequences comprising cattle (10), sheep (12) and goats (11) were retrieved from the GenBank. Forty seven amino acid substitutions of the wild type alleles located in the putative peptide coding region of caprine DQA2 alleles were obtained from the alignment of deduced amino acid sequences of goats. Out of these, eleven amino acid substitutions (H14L, H14R, L34M, E35L, G56S, G56R, 161V, A62E, D69Q, T72N and T72G) were returned neutral;an indication that they did not impair protein function. The Expected Accuracy (EA) ranged from 53% - 87%. For sheep, sixteen amino acid substitutions (A11P, A11T, A11G, A11M, L14S, L14T, V27L, V27S, G35S, S46T, D55E, L57T, L57A, L57G, K65Q and V68I) appeared beneficial while the rest forty seven appeared harmful (EA ranged from 53% - 93%). Twenty four amino acid substitutions did not impair the function of protein while seventy seven substitutions appeared to have a negative effect on the function of protein of cattle (EA ranged from 53% - 94%). The phylogeny based on nucleotide and amino acid sequences of DQA2 gene revealed the close relatedness of the caprine, ovine and bovine species. The present knowledge would be relevant for performing further genotype-phenotype research as well as pharmacogenetics studies in order to show association between caprine, ovine and bovine DQA2 allelic variation and the clinical progression of infectious diseases especially in a developing country such as Nigeria.

不同条件下Co^(2+)对锌电积的影响

Co^(2+)是湿法炼锌中重点关注的有害杂质之一。以含Co^(2+)的硫酸锌溶液作为模拟研究对象,整体研究含Co^(2+)的硫酸锌溶液中分别存在松醇油和Mg^(2+)时,Co^(2+)对锌电解的影响行为。结果表明,当电积液中不存在松醇油和Mg^(2+)时,Co^(2+)的存在造成了锌板的穿孔,出现了轻微“烧板”现象,需要将电积液中Co^(2+)浓度控制在0.6 mg/L以下。当电积液中加入0.21 g/L的松醇油时,Co^(2+)的含量对锌电积的不利影响比电积液中不存在松醇油时的影响更大,需要将电积液中Co^(2+)浓度控制在0.4 mg/L以下。当Mg^(2+)浓度分别为5 g/L和10 g/L时,需要将电积液中Co^(2+)浓度控制在0.4 mg/L和0.2 mg/L以下。当Mg^(2+)浓度为15 g/L时,电积液中的Co^(2+)应尽量除尽。

Influence of CaxSr1-x(0≤x≤1)Substitution for Zn on Microwave Dielectric Properties of Li2ZnTi3O8 Ceramic as Temperature Stable Materials

A temperature stable Li2Zn0.95(SrxCa1-x)0.05Ti3O8(0≤x≤1)ceramics were fabricated using a conventional solid-state route sintered at 1100℃for 4 h.The XRD results indicate that the main phase Li2ZnTi3O8 and secondary phase including SrxCa1-xTiO3(0≤x≤1)solid solution and TiO2 co-exist in composite and form a stable composite system when the(CaxSr1-x)(0≤x≤1)substitutes for Zn of Li2ZnTi3O8 ceramic.As x is increased from 0 to 1,the relative permittivity(εr)increases from 26.65 to 27.12,and the quality factor(Q×f)increases from 63300 to 66600 GHz.With the increased of x,the temperature coefficient of resonant frequency(τf)increases from 0.27 to 8.23 ppm/℃,and then decreases to 3.51 ppm/℃.On the whole,the Li2Zn0.95(SrxCa1-x)0.05Ti3O8(0≤x≤1)ceramics show excellent comprehensive properties of middleεr=25-27,higher Q×f≥60000 GHz andτf≤±8.5 ppm/℃.

Nucleophilic Substitution of Halogenonitrobenzenes by Electrogenerated O_2- on Carbon Gas-diffusion-electrode

Introduction The electrochemical reduction of O;was investigated widely during the past two decades. O;can react with various organic compounds. O;as a new synthesis reagent has been being explored.

Computational Study for the Aromatic Nucleophilic Substitution Reaction on 1-Dimethylamino-2,4-bis(trifluoroacetyl)-naphthalene with Amines

Our previous research showed that aliphatic amines were put in order of high reactivity as “ethylamine > ammonia > t-butylamine > diethylamine” on the aromatic nucleophilic substitution of 1-dimetylamino-2,4-bis(trifluoroacetyl)-naphthalene 1 in acetonitrile. The DFT calculation study (B3LYP/6-31G* with solvation model) for the reactions of 1 with above four amines rationally explained the difference of each amines reactivity based on the energies of their Meisenheimer complexes 3 which are assumed to formed as the reaction intermediates in the course of the reaction giving the corresponding N-N exchange products 2. Intramolecular hydrogen bond between amino proton in 1-amino group and carbonyl oxygen in 2-trifluoroacetyl group stabilizes Meisenheimer complexes 3 effectively, and accelerates the substitution reaction from 1 to 2. Our calculation results also predicted that the above order of amines is also true if less polar toluene is used as a solvent instead of acetonitrile even though more enhanced conditions are required.

Tailoring of Bandgap and Spin-Orbit Splitting in ZrSe_(2) with Low Substitution of Ti for Zr

Tuning the bandgap in layered transition metal dichalcogenides(TMDCs) is crucial for their versatile applications in many fields. The ternary formation is a viable method to tune the bandgap as well as other intrinsic properties of TMDCs, because the multi-elemental characteristics provide additional tunability at the atomic level and advantageously alter the physical properties of TMDCs. Herein, ternary Ti_(x)Zr_(1-x)Se_(2) single crystals were synthesized using the chemical-vapor-transport method. The changes in electronic structures of ZrSe_(2) induced by Ti substitution were revealed using angle-resolved photoemission spectroscopy. Our data show that at a low level of Ti substitution, the bandgap of Ti_(x)Zr_(1-x)Se_(2) decreases monotonically, and the electronic system undergoes a transition from a semiconducting to a metallic state without a significant variation of dispersions of valence bands. Meanwhile, the size of spin-orbit splitting dominated by Se 4p orbitals decreases with the increase of Ti doping. Our work shows a convenient way to alter the bandgap and spin-orbit coupling in TMDCs at the low level of substitution of transition metals.

Impacts of Melt Spinning and Element Substitution on Electrochemical Characteristics of the La–Mg–Ni-based A₂B₇-Type Alloys

The partial substitution of Zr for La has been performed in order to ameliorate the electrochemical hydrogen storage performances of La–Mg–Ni based A2B7-type electrode alloys. The melt spinning technology was used to prepare the La0.75-xZrxMg0.25Ni3.2Co0.2Al0.1 (x=0, 0.05, 0.1, 0.15, 0.2) electrode alloys. The impacts of the melt spinning and the substituting La with Zr on the structures and the electrochemical hydrogen storage characteristics of the alloys were systemically investigated. The analysis of XRD and TEM reveals that the as-cast and spun alloys have a multiphase structure, composing of two main phases (La, Mg)2Ni7 and LaNi5 as well as a residual phase LaNi2. The electrochemical measurement indicates that both the substitution of Zr for La and the melt spinning ameliorate the electrochemical cycle stability of the alloys dramatically. Furthermore, the high rate discharge ability (HRD) of the as-spun (10 m/s) alloys notably declines with growing the amount of Zr substitution, while it first augments and then falls for the (x=0.1) alloy with rising the spinning rate.

Effect of Zn Substitution on Magnetic Properties of CuFe_2O_4： a High-Temperature Series Expansions Study

The magnetic properties of spinel ferrites Cu_（1-x）Zn_xFe_2O_4 are studied using high-temperature series expansions combined with the Padé approximates. The exchange interactions, inter and intra-sublattices J_（AA）, J_（BB） and J_（AB） are obtained using a probability distribution law. The critical exponent associated with the magnetic susceptibility is obtained.

Effect of Substitution Sr Cations on the Structure in the Gd_(1)(Ba_(2−x)Sr_(x))Cu_(3)O_(7−δ) Phases

In an effort to improve the performance of superconductors in the field and high temperatures it is important to study the superconducting mechanism. For this reason, the cation substitution can be conducted. One of the high Tc superconductors Gd1Ba2Cu3O7−δ phase with Sr substitution has been synthesized, i.e. Gd1(Ba2−xSrx)Cu3O7−δ compound. The sample was synthesized by using a solid-state reaction method with a wet mixing, sintered for 12 hours at temperature 900°C. The synthesis results are characterized by using XRD. The results of Match-3 software analysis showed high (higher 85%) Gd1Ba2Cu3O7−δ phase was formed. The Sr substitution causes changes to the structure, i.e. the lattice parameters a, b and c, where the orthorhombicity tends to decrease with increasing Sr content. Refinement results show that based on the oxygen occupancy, the total oxygen content tends to increase.