结构自还原效应对铋掺碱土金属硅磷铝硼玻璃超宽带近红外发光的影响

本文报道了结构自还原对铋掺杂碱土金属硅磷铝硼玻璃超宽带近红外发光性质的影响.以Eu作为对比,在空气气氛中采用高温熔融法分别制备了Eu2O3和Bi2O3掺杂的35SiO2-25AlPO4-12.5Al2O3-12.5B2O3-15RO(R=Ca,Sr,Ba)玻璃.结果证实该玻璃中可发生Eu3+→Eu2+的高温自还原现象,且随着碱土金属离子半径增大Eu2+的自还原性减弱;同样条件下Bi位于1300nm波段的近红外发光却随之增强,而位于1100nm波段近红外发光和源于Bi2+的红光则减弱.根据结构自还原机理及碱土离子半径变化对玻璃近红外超宽带发光性质的影响,讨论了Bi离子的近红外发光中心的归属.上述研究表明玻璃结构自还原特性可以为Bi近红外发光机理研究以及高效Bi掺杂超宽带近红外发光玻璃的设计提供一种有效的思路和方法.

长江口外缺氧区沉积物中元素分布的氧化还原环境效应

对取自长江口外缺氧区及其邻近海域表层沉积物样品进行了粒度组成和元素(主要包括氧化还原敏感性元素和亲碎屑元素)丰度的分析与测试,对长江口外缺氧区缺氧环境对元素分布的影响进行了探讨,提出了长江口外缺氧区沉积物中氧化还原敏感性元素(Redox sensitive elements,简称RSE)分布的氧化还原环境效应。亲碎屑元素丰度的分布显示出明显的粒控效应,而氧化还原敏感元素的分布受粒度效应的制约很弱,主要受离岸缺氧区还原环境的制约,具有在缺氧区富集的特点。缺氧环境对RSE分布的影响超过了元素的粒控效应,从而使研究区RSE的分布呈现出典型的氧化还原环境效应。

钛精矿球磨活化微波还原试验

研究攀枝花低品位钛精矿的球磨活化-微波还原。采用激光粒度及X衍射研究不同球磨条件下钛铁矿的粒度和物相变化并进行分析,结果表明磨矿活化使矿物颗粒逐渐减小、特征峰宽化、晶粒变细;研究了活化物料的升温和还原行为,并对还原产物微观形貌和物相进行分析,表明活化物料有良好的微波吸收性能和还原效应。证实在反应过程中存在"热点"。球磨8 h的混合物料在温度900℃、反应时间30 m in条件内金属化率超过90%。

还原体(体系)与富铀矿的形成

铀是变价元素,还原体(体系)在铀富集过程中起着相当重要的作用。还原体(体系)可分两类:一类为自还原体(体系),这是指还原体(剂)是热液本身的还原体系,还原剂和铀在同一热液体系中搬运、迁移,然后在变化了的物理化学条件下,铀依靠热液本身的还原性能而被还原沉淀。另一类为外部还原体系,这是指铀的沉淀的还原作用是依靠围岩中的还原剂或地球化学场。两类还原体(体系)对铀的富集成矿具有不同方式,从而有不同的地质环境要求。

Cation effects in electrocatalytic reduction reactions:Recent advances

Electrocatalytic reduction reactions,powered by clean energy sources such as solar energy and wind,offer a sustainable method for converting inexpensive feedstocks(e.g.,CO_(2),N2/NOx,organics,and O_(2))into high-value-added chemicals or fuels.The design and modification of electrocatalysts have been widely implemented to improve their performance in these reactions.However,bottle-necks are encountered,making it challenging to further improve performance through catalyst development alone.Recently,cations in the electrolyte have emerged as critical factors for tuning both the activity and product selectivity of reduction reactions.This review summarizes recent advances in understanding the role of cation effects in electrocatalytic reduction reactions.First,we introduce the mechanisms underlying cation effects.We then provide a comprehensive overview of their application in electroreduction reactions.Characterization techniques and theoretical calcula-tion methods for studying cation effects are also discussed.Finally,we address remaining challeng-es and future perspectives in this field.We hope that this review offers fundamental insights and design guidance for utilizing cation effects,thereby advancing their development.

海明威小说手法研究

冰山理论是海明威提出的重要创作理念,他成功地将这一理念运用到自己的创作实践中,叙述简略扼要、浓缩紧凑,采用不带个人感情色彩的平淡而克制的陈述来渲染气氛,并且对经验加以吸收、消化,省略掉人所共知的东西。省略在这里是一种经验省略,以达到主体隐退的效果,省略的东西是可以利用经验加以填补的,其目的是营造出一种真实的艺术效果,并不等同于传统的留白手法所营造的含混的意蕴。海明威对自己省略手法的打磨,使得其作品表现出一种还原"效应",不仅净化了文风,删去了不必要的枝节,还原了基本枝干的清爽面目,而且高度准确地描摹了生活本身,运用简单的对话和细节描写,剥离了文字的印象,出脱出一种油画的效果。

Ag-Ni alloy nanoparticles for electrocatalytic reduction of benzyl chloride

Ag-based nanocatalysts exhibit good catalytic activity for the electrochemical reduction of organic halides. Ag-Ni alloy nanoparticles（NPs） were facilely prepared by chemical reduction, and the as-prepared nanocatalysts were characterized by X-ray diffraction, ultraviolet-visible spectroscopy, transmission electron microscopy and energy-dispersive X-ray spectroscopy. The electrocatalytic activity of Ag-Ni NPs for benzyl chloride reduction was studied in organic medium using cyclic voltammetry, chronoamperometry and electrochemical impedance spectroscopy. The results show that the addition of Ni element can obviously decrease the size of Ag-Ni NPs, shift the reduction peak potential（φp） of benzyl chloride positively, and increase the catalytic activity of Ag-Ni NPs. However, when the Ni content reaches a certain value, the catalytic activity of Ag-Ni NPs decreases. Meanwhile, the synergistic catalytic effect of Ag-Ni NPs was also discussed.

简析沉淀──溶解的本质

本文剖析了沉淀溶解的本质，分析了促使沉淀溶解的因素，为寻找合适的溶剂提供了理论依据。

Substituent Effects on Reduction Potentials of Meta-substituted and Para-substituted Benzylideneanilines

Effects of meta-substituent of 3,4＇/4,3＇/3,3＇-substituted benzylideneanilines （XBAYs） on the electrochemical reduction potentials （E（Red）） were investigated, in which 49 samples of target compounds were synthesized, and their reduction potentials were measured by cyclic voltammetry. The substituent effects on the E（Red） of target compounds were analyzed and an optimality equation with four parameters （Hammett constant a of X, Hammett constant a of Y, excited-state substituent constant σexCC of X, and the substituent specific cross-interaction effect △σexCC2 between X and Y） was obtained. The results show that the factors affecting the E（Red） of 3,4＇/4,31/3,3P-substituted XBAYs are different from those of 4,4＇-substituted XBAYs. For 3,4＇/4,3＇/3,3＇-substituted XBAYs, σ（X） and σ（Y） must be employed, and the contribution of △σexCC2 is important and not negligible. Compared with 4,4＇-substituted XBAYs, X group contributes less to 3,4＇/4,3＇/3,3＇-substituted XBAYs, while Y group contributes more to them. Additionally, it was observed that either para-substituted XBAYs or meta-substituted XBAYs, the substituent effects of X are larger than those of Y on the E（Red） of substituted XBAYs.

Amorphous CoOx coupled carbon dots as a spongy porous bifunctional catalyst for efficient photocatalytic water oxidation and CO2 reduction

Cobalt-based oxides,with high abundance,good stability and excellent catalytic performance,are regarded as promising photocatalysts for artificial photosynthetic systems to alleviate foreseeable energy shortages and global warming.Herein,for the first time,a series of novel spongy porous CDs@CoOx materials were synthesized to act as an efficient and stable bifunctional photocatalyst for water oxidation and CO2 reduction.Notably,the preparation temperatures visibly influence the morphologies and photocatalytic performances of the CDs@CoOx.Under the optimal conditions,a maximum O2 yield of 40.4% and pretty apparent quantum efficiency(AQE)of 58.6% at 460 nm were obtained over CDs@CoOx-300 for water oxidation.Similarly,the optimized sample CDs@CoOx-300 manifests significant enhancement on the CO2-to-CO conversion with a high selectivity of 89.3% and CO generation rate of 8.1μmol/h,which is superior to most previous cobalt-based catalysts for CO2 reduction.The composite CDs@CoOx-300 not only exposes more active sites but also facilitates electron transport,which results in excellent photocatalytic activity.In addition,the boosted photocatalytic behavior is attributed to the synergistic effect between CoOx and CDs,which was verified by the photocatalytic activity control experiments and electrochemical characterization.The work offers a novel strategy to fabricate a high performance bifunctional photocatalyst for water oxidation and CO2 reduction.

Nonlinear effect induced in thermally poled glass waveguides

Thermally poled germanium-doped channel waveguides are presented. Multilayer waveguides containing a silicon oxynitride layer were used as charge trapper in this investigation on the effect of the internal field inside the waveguide. Compared to waveguides without the trapping layer, experimental results showed that the induced linear electro-optic (EO) coefficient increases about 20% after poling, suggesting strongly that the internal field is relatively enhanced, and showed it is a promising means for improving nonlinearity by poling in waveguides.

Reveal the nature of particle size effect for CO_(2) reduction over Pd and Au

Small cluster and periodic surface models with low coverages of intermediates are frequently employed to investigate reaction mechanisms and identify active sites on nanoparticles(NPs)in density functional theory(DFT)studies.However,diverse active sites on NPs cannot be sufficiently represented by these simple models,hampering the in-depth insights into the catalytic behavior of NPs.This paper describes the crucial roles of both model and coverage effect on understanding the nature of active sites for CO_(2)reduction over Au and Pd NPs using DFT calculations.Terrace sites exhibit higher selectivity for CO than edge sites on Au NPs,which is opposite to the results on Au periodic surfaces.This contradiction reveals the computational model effect on clarifying active site properties.For Pd catalysts,the coverage effect is more significant.On bare Pd NPs and periodic surfaces,the selectivity for CO at edge sites is nearly identical to that at terrace sites,whereas edge sites display higher selectivity for CO than terrace sites in the case of high CO coverages.Through considering the more realistic models and the coverage effect,we successfully describe the size effect of Au and Pd NPs on CO selectivity.More importantly,this work reminds us of the necessity of reasonable models in DFT calculations.

Redox chemistry of N_(4-)Fe^(2+)in iron phthalocyanines for oxygen reduction reaction

A precise understanding of the redox chemistry of Nm-Mn+(like N4-Fe^(2+))systems is essential for fundamental studies and rational design of Nm-Mn+-based electrocatalysts for the oxygen reduction reaction(ORR).Herein,three different iron phthalocyanines(FePcs)adsorbed on carbon nanotubes((NH2)4FePc@CNTs,(t-Bu)4FePc@CNTs,and FePc@CNTs)were evaluated to demonstrate the effect of the electron donating power of the substituents on the Fe^(3+)/Fe^(2+)redox potential of FePc@CNTs and the role of these composites as ORR mediators in alkaline media.The Fe^(3+)/Fe^(2+)redox potential of the FePcs was found to shift towards the cathodic region upon substitution with electron-donating groups.This up-field shift in the eg-orbital leads to a lower overlap between the onset potential of the Fe^(3+)/Fe^(2+)redox couple and that of the ORR,and thus,the ORR activity decreased in the following order based on the substitution of FePc:-H>-t-Bu>-NH2.

Recent progress in electronic modulation of electrocatalysts for high-efficient polysulfide conversion of Li-S batteries

With the merits of high energy density,environmental friendliness,and cost effectiveness,lithium-sulfur(Li-S)batteries are considered as one of the most promising next-generation electrochemical storage systems.However,the notorious polysulfide shuttle effect,which results in low active material utilization and serious capacity fading,severely impedes the practical application of Li-S batteries.Utilizing various electrocatalysts to improve the polysulfide redox kinetics has recently emerged as a promising strategy to address the shuttle effect.Specially,the electronic structure of the electrocatalysts plays a decisive role in determining the catalytic activity to facilitate the polysulfide conversion.Therefore,reasonably modulating the electronic structure of electrocatalysts is of paramount significance for improving the electrochemical performance of Li-S batteries.Herein,a comprehensive overview of the fascinating strategies to tailor the electronic structure of electrocatalysts for Li-S batteries is presented,including but not limited to vacancy engineering,heteroatom doping,single atom doping,band regulation,alloying,and heterostructure engineering.The future perspectives and challenges are also proposed for designing high-efficient electrocatalysts to construct high-energy-density and long-lifetime Li-S batteries.

MOSSBAUER STUDY ON REDUCIBILITY OF SUPPORTED Eu_2O_3

The reduction process of Eu2O3 on TiO2 and other supports is investigated in detail by Mossbauer spectroscopy. The reducibility of Eu2O3 is greatly enhanced when it is supported on a surface of support. This is due to the solid-solid interaction between the oxide and the support.

Dual-site collaboration boosts electrochemical nitrogen reduction on Ru-S-C single-atom catalyst

Electrocatalytic reduction of nitrogen into ammonia(NH_(3))is a highly attractive but challenging route for NH_(3)production.We propose to realize a synergetic work of multi reaction sites to overcome the limitation of sustainable NH_(3)production.Herein,using ruthenium-sulfur-carbon(Ru-S-C)catalyst as a prototype,we show that the Ru/S dual-site cooperates to catalyse eletrocatalytic nitrogen reduction reaction(eNRR)at ambient conditions.With the combination of theoretical calculations,in situ Raman spectroscopy,and experimental observation,we demonstrate that such Ru/S dual-site cooperation greatly facilitates the activation and first protonation of N_(2)in the rate-determining step of eNRR.As a result,Ru-S-C catalyst exhibits significantly enhanced eNRR performance compared with the routine Ru-N-C catalyst via a single-site catalytic mechanism.We anticipate that our specifically designed dual-site collaborative catalytic mechanism will open up a new way to offers new opportunities for advancing sustainable NH_(3)production.

Electrochemical Study on Hydrogen Evolution and CO2 Reduction on Pt Electrode in Acid Solutions with Different pH

Hydrogen evolution reaction(HER)is the major cathodic reaction which competes CO2 reduction reaction(CO2 RR)on Pt electrode.Molecular level understanding on how these two reactions interact with each other and what the key factors are of CO2 RR kinetics and selectivity will be of great help in optimizing electrolysers for CO2 reduction.In this work,we report our results of hydrogen evolution and CO2 reduction on Pt(111)and Pt film electrodes in CO2 saturated acid solution by cyclic voltammetry and infrared spectroscopy.In solution with pH>2,the major process is HER and the interfacial pH increases abruptly during HER;COad is the only adsorbed intermediate detected in CO2 reduction by infrared spectroscopy;the rate for COad formation increases with the coverage of UPD-H and reaches maximum at the onset potential for HER;the decrease of COad formation under HER is attributed to the available limited sites and the limited residence time for the reduction intermediate(Had),which is necessary for CO2 adsorption and reduction.

Investigation of lattice capacity effect on Cu2+-doped SnO2 solid solution catalysts to promote reaction performance toward NOx-SCR with NH3

To understand the effect of the doping amount of Cu^2+ on the structure and reactivity of SnO2 in NOx-SCR with NH3, a series of Sn-Cu-O binary oxide catalysts with different Sn/Cu ratios have been prepared and thoroughly characterized. Using the XRD extrapolation method, the SnO2 lattice capacity for Cu^2+ cations is determined at 0.10 g Cu O per g of SnO2, equaling a Sn/Cu molar ratio of 84/16. Therefore, in a tetragonal rutile SnO2 lattice, only a maximum of 16% of the Sn4+ cations can be replaced by Cu^2+ to form a stable solid solution structure. If the Cu content is higher, Cu O will form on the catalyst surface, which has a negative effect on the reaction performance. For samples in a pure solid solution phase, the number of surface defects increase with increasing Cu content until it reaches the lattice capacity, as confirmed by Raman spectroscopy. As a result, the amounts of both active oxygen species and acidic sites on the surface, which critically determine the reaction performance, also increase and reach the maximum level for the catalyst with a Cu content close to the lattice capacity. A distinct lattice capacity threshold effect on the structure and reactivity of Sn-Cu binary oxide catalysts has been observed. A Sn-Cu catalyst with the best reaction performance can be obtained by doping the SnO2 matrix with the lattice capacity amount of Cu^2+.

Fabricating high-loading Fe-N4 single-atom catalysts for oxygen reduction reaction by carbon-assisted pyrolysis of metal complexes

Iron-based single-atom catalysts with nitrogen-doped carbon as support(Fe-SA/NPC)are considered effective alternatives to replace Pt-group metals for scalable application in fuel cells.However,synthesizing high-loading Fe-SA catalysts by a simple procedure remains challenging.Herein,we report a high-loading(7.5 wt%)Fe-SA/NPC catalyst prepared by carbon-assisted pyrolysis of metal complexes.Both the nitrogen-doped porous carbon(NPC)support with high specific surface area and ο-phenylenediamine(o-PD)play key roles role in the preparation of high-loading Fe-SA/NPC catalysts.The results of X-ray photoelectron spectroscopy,high-angle annular dark-field scanning transmission electron microscopy,and X-ray absorption fine structure spectroscopy experiments show that the Fe atoms are anchored on the carbon carriers in a single-atom site configuration and coordinated with four of the doped nitrogen atoms of the carbon substrates(Fe-N_(4)).The activities of the Fe-SA/NPC catalysts in the oxygen reduction reaction increased with increasing iron loading.The optimized 250Fe-SA/NPC-800 catalyst exhibited an onset potential 0.97 V of and a half-wave potential of 0.85 V.Our study provides a simple approach for the large-scale synthesis of high-loading single-atom catalysts.

One-pot synthesis of mesosilica/nano covalent organic polymer composites and their synergistic effect in photocatalysis

Organic-inorganic hybrid materials provide a desirable platform for the development of novel functional materials.Here,we report the one-pot synthesis of mesoporous hybrid nanospheres by the in-situ sol-gel condensation of tetraethoxysilane around surfactant micelle-confined nano covalent organic polymer(nanoCOP)colloids.The hybrid nanospheres containing nanoCOPs uniformly distributed in the mesosilica network,inherited the visible light responsive properties of the nanoCOPs.The turnover frequency of the hybrid nanospheres is almost 12 times that of its corresponding bulk COP counterpart for the photocatalytic reductive dehalogenation of a-bromoacetophenone,which is attributed to activation of the Hantzsch ester reductant by the hydroxyl group.The existence of a volcano relationship between the activity and nano COP/mesosilica ratio confirmed the synergistic effect between nano COP and mesosilica.Our preliminary results suggest that hybridization of semiconductors and reactant-activating materials is an efficient strategy for enhancing the activity of a catalyst for photocatalysis.