Buffer anion effects on water oxidation catalysis: The case of Cu(Ⅲ) complex

Water oxidation is the bottleneck of artificial photosynthesis.Since the first ruthenium-based molecular water oxidation catalyst,the blue dimer,was reported by Meyer’ s group in 1982,catalysts based on transition metals have been widely employed to explore the mechanism of water oxidation.Because the oxidation of water requires harsh oxidative conditions,the stability of transition complexes under the relevant catalytic conditions has always been a challenge.In this work,we report the redox properties of a CuⅢ complex(TAML-CuⅢ] with a redox-active macrocyclic ligand(TAML) and its reactivity toward catalytic water oxidation.TAML-CuⅢ displayed a completely different electrochemical behavior from that of the TAML-CoⅢ complex previously reported by our group.TAML-CuⅢ can only be oxidized by one-electron oxidation of the ligand to form TAML·+-CuⅢand cannot achieve water activation through the ligand-centered proton-coupled electron transfer that takes place in the case of TAML-CoⅢ.The generated TAML·+-CuⅢ intermediate can undergo further oxidation and ligand hydrolysis with the assistance of borate anions,triggering the formation of a heterogeneous B/CuOx nanocatalyst Therefore,the choice of the buffer solution has a significant influence on the electrochemical behavior and stability of molecular water oxidation catalysts.

Gradual or Hysteretic Transition:Anion Effects on Cobalt(II)Spin Crossover Complexes

Comprehensive Summary To better understand the impact of different anions on the structures and SCO properties of the CoII SCO complexes,six new complexes[Co(terpy-CH_(2)OH)_(2)]A_(2)·sol(terpy-CH_(2)OH=4′-(hydroxymethyl)-2,2′;6′,2″-terpyridine,A=Br–(1,sol=1.5H_(2)O),I–(2),N3–(3,sol=2H_(2)O),H_(3)BCN–(4),OTf–(5),and TsO–(6,sol=4H_(2)O·CH_(3)CN),have been synthesized and characterized.All six compounds consist of mononuclear[Co(terpy-CH_(2)OH)_(2)]^(2+)cations and charge-balancing anions that differ in size,shape,and hydrogen bonding capacity.Complexes 1,2,3,and 6 displayed incomplete gradual SCO transitions,whereas 4 and 5 exhibited abrupt hysteretic spin transitions with loops of 12 and 16 K(250.0—262.0 K for 4,and 370.0—386.0 K for 5,respectively),closely resembling our previously reported complexes with SCN^(–)and SeCN^(–)anions.The occurrence of the order-disorder transition of the CH2OH groups and their transition temperatures are determined by the size and hydrogen bonding capability of the anions.Remarkably,the transition temperatures of complexes with H_(3)BCN^(–),SCN^(–),OTf^(–),and SeCN^(–)anions exhibit an upward trend as the size and mass of the anions increase,as confirmed through detailed single crystal structure analyses conducted in both high-spin and low-spin states for all four complexes.

Effect of Competing Anions on Arsenate Adsorption onto Maghemite Nanoparticles

This paper reports the effect of several competing anions on arsenate adsorption with maghemite nanoparticles. Sulphate （as SO4）, nitrate （as NO3-N）, phosphate （as PO4-P） ions and silicate-（as SiO2） were-studied in dual solution with arsenate. Moreover, the combined effect of ions and other water characteristics were examined with a natural groundwater sample which was spiked with a certain amount of arsenate. Arsenate batch adsorption experiments were carried out with two different kinds of maghemite-a commercially, available one and a homemade one using the sol-gel orocess. Sulohate （≤250 mg.L-1） and nitrate （≤ 12 mg.L-1） had a neglivible effect onthe arsenate （0.5 mg.L-1） adsorption at pH 3. However, both phosphate （42.9 mg·L-1） and silicate （450 mg.L-j） had an adverse impact on arsenate （43 mg.L-1） adsorption at pH 7. Phosphate （41.5 mg.L-1） showed minimal competition with arsenate （0.5 mg.L-1）, while silicate （410 mg.L-1） inhibition was insignificant for all studied As（V） concentrations at p.H 3. The removal of arsenate from the groundwater sample was as efficient as from labo-ratory water tor 0.3 mgL -1 AS（V） botll at pH3 and pH7.

Study on Inhibition Effects of Rare Earths on Superoxide Anion Radical by Using Pulse Radiolysis

The inhibition effect of rare earths on the production of ·O - 2 produced by radiolysis of aqueous sodium formate saturated with O 2 with high energy pulse electron beam was studied. The result indicates that rare earth nitrate obviously inhibits the production of ·O - 2 . The inhibition rate is between 28 6% and 92%. The inhibition effect increases with the increase of rare earth nitrates concentration. The distinguish dose effect relationship was observed.

Theoretical Study of Halogen Effect in Isomerization of 2-Halo-[9]-annulen Anion at the DFT Level

Cis-trans isomerization of [9]-annulenanion（1） and its 2-fluoro-,2-chloro-and 2-bromo-derivatives（2,3 and 4,respectively） were investigated at the HF/6-31G＊ and B3LYP/6-311＋＋G＊＊ levels of theory.Cis,cis,cis,cis structures appear more stable than their corresponding cis,cis,cis,trans-isomers.The relative height of energy barriers for cis-trans isomerization is：2cis 〉1cis 〉3cis〉 4cis.This trend for the reverse trans-cis isomerization follows the electronegativity of the substituent at C-2（2trans 3trans 4trans 1trans）.

Anion type-dependent confinement effect on glass transitions of solutions of LiTFSI and LiFSI

We present findings on the effect of nanometer-sized silica-based pores on the glass transition of aqueous solutions of lithium bis(trifluoromethane)sulfonimide(LiTFSI)and lithium difluorosulfimide(LiFSI),respectively.Our experimental results demonstrate a clear dependence of the confinement effect on the anion type,particularly for water-rich solutions,in which the precipitation of crystalized ice under cooling process induces the formation of freeze-concentrated phase confined between pore wall and core ice.As this liquid layer becomes thinner,the freeze-concentrated phase experiences glass transition at increasingly higher temperatures in solutions of LiTFSI.However,differently,for solutions of LiFSI and LiCl,this secondary confinement has a negligible effect on the glass transition of solutions confined wherein.These different behaviors emphasize the obvious difference in the dynamic properties’response of LiTFSI and LiFSI solutions to spatial confinement and particularly to the presence of the hydrophilic pore wall.

OPTICAL EFFECTS OF ANION ADSORPTION ON SILVER SOL

The optical effects of anion adsorption on silver sol have been studied, It was found that the anion adsorption can make the absorption peak of pure silver sol shifting to longer vevelenngth, which is attributed to the reduction of the free electron density in the surface layer of the silver particle.

Effects of thiocyanate anions on switching and structure of poly(N-isopropylacrylamide) brushes

In this work, we investigate the effects of thiocyanate anions on the switching and the structure of poly(Nisopropylacrylamide)(PNIPAM) brushes using a molecular theory. Our model takes into consideration the PNIPAM–anion bonds, the electrostatic effects and their explicit coupling to the PNIPAM conformations. It is found that at low thiocyanate anion concentration, as the anion concentration of thiocyanate increases, thiocyanate anions are more associated with PNIPAM chains through the PNIPAM–anion bonds, which contributes to stronger electrostatic repulsion and leads to an increase of lower critical solution temperature(LCST). By analyzing the average volume fractions of PNIPAM brushes,it is found that the PNIPAM brush presents a plateau structure. Our results show that the thiocyanate anions promote phase segregation due to the PNIPAM–anion bonds and the electrostatic effect. According to our model, the reduction of LCST can be explained as follows: at high thiocyanate anion concentration, with the increase of thiocyanate concentration, more ion bindings occurring between thiocyanate anions and PNIPAM chains will result in the increase of the hydrophobicity of PNIPAM chains;when the increase of electrostatic repulsion is insufficient to overcome the hydrophobic interaction of PNIPAM chains, it will lead to the reduction of brush height and LCST at high thiocyanate anion concentration. Our theoretical results are consistent with the experimental observations, and provide a fundamental understanding of the effects of thiocyanate on the LCST of PNIPAM brushes.

Toxic Effects of an Anionic Detergent on the Lipid Constituents of Various Cell Types of the Gill Epithelium of Rita rita:A Histochemical Investigation

Rita rita exposed to a concentration of 6.9 mg per liter(96-h LC_(50)of an anionic detergent, dodecylbenzene sodium sulfonate)exhibited a gradual decrease in the lipid moieties of the epi- thelial cells,club cells,and goblet mucous cells lining the gill arch and gill filament epithelium. However,in time,no reaction of any of the lipid moieties could be observed,indicating the absence of the same,using various histochemical techniques.The results are discussed in light of the mechanistic understanding of detergent action.1989 Academic Press,Inc.

Effects of Electrolyte Anions and pH on Adsorption of Snlfate by Variable Charge Soils

The effects of three electrolyte anions, ionic strength and pH on the adsorption of sulfate by two variablecharge soils, with different surface charge properties were studied. Under the conditions of the same pHand ionic strength the effect of electrolyte anions on the adsorption of sulfate was in the order of , indicating the difference of the nature among these three anions. For Ferralsol in the sameconcentration of chloride and perchloride solutions, the two sulfate adsorption-pH curves could intersectat certain pH value. When pH was higher than the intersecting point, more sulfate was adsorbed in theperchloride solution, while when it was lower than the intersecting point, more sulfate was adsorbed in thechloride solution. In different concentrations of electrolyte solution, the curves of the amount of oxy-acidanion adsorbed, which changed with pH, could intersect at a certain pH, which is termed point of zero salteffect （PZSE） on adsorption. The nature of electrolyte anions influenced obviously the appearance of PZSEfor sulfate adsorption. For ferraisol the curves of adsorption converged to about pH 7 in NaCl solution seemedto intersect in NaNO3 solution and to have a typical PZSE for sulfate adsorption in NaClO4 solution. ForAcrisol the three curves of adsorption were nearly parallel in NaCl and NaNO3 solutions and converged topH 6.5 in NaClO4 solution.

Effect of Sulfate Adlayer on Formic Acid Oxidation on Pd(111) Electrode

The kinetics of formic acid oxidation (FAO) on Pd(111) in 0.1 mol/L H2SO4+0.1 mol/L HCOOH with and without addition of Na2SO4 is studied using cyclic voltammetry and potential step method, which is compared with that in 0.1 mol/L HClO4. It is found that adsorbed sulfate has significant inhibition effect on FAO kinetics. After addition of 0.05 mol/L or 0.1 mol/L Na2SO4, FAO current in the negative-going scan is found to be significantly smaller than that at the same potential in the positive-going scan. We speculate that at potentials positive of the phase transition potential for the (SO4*ad)m+[(H2O)n-H3O+] or(SO4*ad)m+[Na+(H2O)n-H3O+] adlayer, the adlayer structure probably becomes denser and more stable with the increase of potential or with the addition of Na2SO4. The formation of connected adlayer network greatly enhance the stability of the adlayer, and the insertion of positive-charged H+ or Na+ into the adlayer network further reduces the electrostatic repulsion between partially charged sulfates. As a result, the destruction/desorption of compact sulfate adlayer becomes more difficult, which leaves much less free sites on the surface for FAO, and thus FAO kinetics at higher potentials and in the subsequent negative-going potential scan is significantly inhibited.

Topomerization of 2-Halo-[9] Annulen Anion at the DFT Level

Topomerization of [9] annulen anion （1） and its 2-fluoro-, 2-chloro- and 2- bromo-defivatives （2, 3 and 4, respectively） are studied at the HF/6-31G＊ and B3LYP/6-31 1＋＋G＊＊ levels of theory. The relative ease of topomerization is dependent on the charge distribution and planarity of the ground state and the transition state of 9-membered rings as well as the size and electronegativity of halogen substituent. Consequently, the endo-2-halo-[9] annulen anion topomers become unstable and easily convert to related exo-topomers. Hence, according to the DFT calcu- lations, the order of topomerization energy barrier for endo = exo topomerization is lendo 〉 2endo 〉 3endo.

CO2 Capture at Room Temperature and Ambient Pressure: Isomer Effect in Room Temperature Ionic Liquid/Propanol Solutions

A CO2 capture system without supercritical CO2 was optimized for mixtures of hydrophobic room temperature ionic liquids (RTILs) and propanol. We tested RTILs using bis(trifluoromethanesulfonyl)imide, TFSI-, anion and four quaternary ammonium cations, two quaternary phosphonium cations, and one imidazolium cation. The addition of 2-propanol into the RTILs clearly promoted the capture of normal CO2(nCO2) at ambient temperature and pressure. When combined with 2-propanol, the most efficient RTILs for nCO2 capture were N-butyl-N,N,N-trimethylammonium TFSI-. This enhancement of nCO2 capture was not observed in RTIL mixtures with 1-propanol or in propanol mixtures containing other phosphonium- and imidazolium-based RTILs. The torsion angle of TFSI-, which was calculated using density functional theory, is thought to be related to high nCO2 capture efficiently.

Theoretical Investigations of Nonlinear Optical Properties of Transition Metal Cluster Anions

In the framework of density functional theory （DFT）, the electronic excitations and nonlinear optical （NLO） properties of six binuclear transition metal cluster anions with the formula of [Ch2M-（μ-Ch）2-M＇CN]^2- （M = Mo, W; Ch = S, Se; M＇ = Cu, Ag） have been systemically investigated at both cases of gas phase and DMF solution. The obtained electronic absorption spectra reveal that the element replacements of metals M and ligands Ch have significant influence on the absorptions, especially on the low-lying ones. In addition, the transitions of μ-Ch→M are dominant for the low-lying excitations, whereas the transitions of M＇→M as well as Ch→M are mainly responsible for the higher excitations. The calculated molecular first and second hyperpolarizabilities present the remarkable element substitution and solvent effects. The analyses show that the transitions involving μ-Ch→M charge transfer make the critical contributions to the first hyperpolarizability t, and that the charge transfers from the moieties of MCh4 to M＇CN as well as those of μ-Ch→M and M＇→M are responsible for the second hyperpolarizability y. Moreover, the introduction of solvent leads to the results that the transitions within the moieties of MCh4 and M＇CN make larger contributions to the hyperpolarizability, especially to γ.

阴阳离子组合捕收剂在低品位锂云母矿浮选回收中的应用及选择性吸附机理研究

针对强酸性矿浆体系(pH=2~3)胺类捕收剂浮选锂云母矿时,存在硫酸耗量高、设备腐蚀严重、浮选泡沫黏度大、废水处理困难等问题,以湖南某含钨锡锂铷多金属矿的钨锡选别尾矿(锂云母浮选给矿,Li_(2)O品位0.44%)为研究对象,在中性矿浆环境和不脱泥条件下,采用阴离子捕收剂WJ和阳离子捕收剂DDA(十二胺)组合对该低品位锂云母矿进行浮选回收,并通过原子力显微镜和芘荧光光谱从微观层面探究了阴阳离子组合捕收剂的协同效应与吸附机理。结果表明:相比单一DDA,采用WJ+DDA组合(质量比3.5∶1),捕收剂用量降低130 g/t,获得的锂云母精矿中Li_(2)O品位提高0.35%,Li_(2)O回收率提高1.41%,且浮选泡沫清爽,脉石夹带少。WJ+DDA组合捕收剂分子更密集地吸附在锂云母表面,而在石英/长石表面基本不发生吸附。相比单一WJ或DDA,WJ+DDA组合捕收剂具有更大的非极性和更强的疏水性,因而具有更高的表面活性。

阴离子对鼠尾草提取物中Ni盐前体绿色合成的NiO纳米粒子磁性和结构性能的影响

采用绿色合成方法,将鼠尾草提取物用作还原和封端剂合成氧化镍纳米颗粒(NiO NPs)。此外,使用各种前驱体合成了NiO NPs,并使用扫描电子显微镜对其形貌进行了分析。利用傅里叶变换红外光谱和粉末X射线衍射(PXRD)对NiO NPs的结构进行了表征,使用振动样品磁强计测量了它们的磁性。PXRD研究表明,所有合成的NiO NPs都表现出具有高结晶度的面心立方相,并且形成了具有高纯度相的NiO。磁化研究结果表明,3种镍盐(乙酸盐、氯化物和硫酸盐)前驱体合成的NiO NPs分别表现出超顺磁、软铁磁和顺磁行为。

疏水修饰纳米颗粒强化天然气泡沫的稳定性及影响因素

为了增强天然气泡沫在提高采收率中的应用效果,采用注射法研究了疏水修饰纳米颗粒(HMNP)与不同类型表面活性剂复合生成的天然气泡沫的稳定性及温度、无机盐(NaCl、CaCl_(2))对天然气泡沫稳定性的影响机制。结果表明:在室温(25℃)纯水条件下,HMNP与阴离子表面活性剂(十二烷基磺酸钠(SDS)、十二烷基苯磺酸钠(SDBS)、十二烷基聚氧乙烯醚硫酸钠(AES))复合体系生成的天然气泡沫在3000 min内可保持很好的稳定性,具有显著协同稳定天然气泡沫稳定性的作用。而且,在50℃条件下或离子强度为0.2 mol/L的情况下,阴离子表面活性剂中的聚氧乙烯(EO)基团可以进一步增强HMNP/AES复合体系天然气泡沫的稳定性及耐温耐盐性;阴离子表面活性剂中的苯环则可显著促进HMNP与阴离子表面活性剂的协同效应,更大幅度提高HMNP/SDBS复合体系天然气泡沫的稳定性、耐温性及耐一价金属离子能力。

低泡表面活性剂CYS在印染前处理中的应用性能研究

本研究对采用SO3膜式磺化工艺制备的特种醇醚硫酸盐阴离子表面活性剂CYS-221进行了性能研究,测定了CYS-221的表面张力、泡沫、乳化、不同浓度产品黏度、毛细效应,并与常规阴离子表面活性剂AES、非离子表面活性剂AEO-9、1309进行了比较。结果表明:CYS-221泡沫低于AES、AEO-9、1309;CYS-221乳化能力优于AES、AEO-9、1309;CYS-221稀释过程凝胶区窄;经CYS-221处理后的坯布毛细效应高于AES和1309。

天目山不同海拔柳杉群落特征与空气负离子效应分析

选择天目山国家森林公园不同海拔高度的9个古柳杉群落为研究对象,调查柳杉群落种类组成、结构、外貌特征,实测春夏秋三季不同柳杉生境小气候、空气负离子浓度的瞬时值,并评价其空气清洁度。结果表明:在生长季节,随着海拔高度增加柳杉群落Simpson、Shannon-Wienner及Pielou等多样性指数均呈增长趋势,大小排序为山顶(0.918 2;4.345 9;0.805 9)>山麓(0.895 9;4.116 0;0.781 1)>山中(0.890 9;3.999 6;0.747 3),而植物群落物种丰富度指数则表现不同特点,其增长趋势为山中(37)>山顶(33)>山麓(31);春夏季节空气负离子浓度日变化呈双峰曲线,而秋季空气负离子浓度则呈单峰曲线。随着海拔高度增加空气负离子浓度呈上升趋势,且山顶、山中较高海拔的柳杉群落空气负离子浓度显著高于山麓,其CI值(空气质量评价指数)也高于山麓。

阴离子对嗜酸氧化亚铁硫杆菌生长和硫氧化活性的影响

以嗜酸氧化亚铁硫杆菌(Acidithiobacillus ferrooxidans,ATCC23270)为对象,研究NO3-、SO42-、Cl-和PO43-对Acidithiobacillus ferrooxidans生长和硫氧化活性的影响。结果表明:不同阴离子对Acidithiobacillus ferrooxidans硫氧化表观活性的影响效应不同,其影响由大到小的顺序依次为Cl-,NO3-,SO42-和PO43-;在高浓度PO43-的胁迫(300mmol/L)下,细菌所表达蛋白质的总数量减少,但同时表达一些特异性蛋白质,这说明细菌可通过抑制一些在正常条件下表达的蛋白质,同时表达一些新的蛋白质来应对无机离子的胁迫效应。