Tuning electronic structure ofδ-MnO_(2) by the alkali-ion(K,Na,Li)associated manganese vacancies for high-rate supercapacitors

Cation vacancies can bring numerous surprising characters due to its multifarious electron and orbit distribution.In this work,d-MnO_(2) with alkali-ion(K,Na,Li)associated manganese(Mn)vacancies is fabricated by a simple hydrothermal reaction,and the correlation between their electronic structure and pseudocapacitance are systematically investigated.FESEM/TEM images have shown that the morphology of MnO_(2) is obviously changed after the introducing of cation vacancies.The position of alkali-ion in MnO_(2) structure can be controlled by adjusting the ion concentration.XRD patterns and Raman spectra demonstrate that the alkali-ion is embedded in Mn vacancies at low concentration,while entered the interlayer of MnO_(2) at high concentration.The existence of Mn vacancies will resulting in the distortion of neighboring atoms,leading to the electronic delocalization,and thus enhancing the conductivity,pseudocapacitance and rate capability of MnO_(2).Accordingly,the specific capacitances of optimized 0.4 KMO,0.4 NaMO and 0.4 LiMO samples are enhanced about 1.9,1.6 and 1.6 times compared to pure MnO_(2).Meanwhile,the rate performance has also been improved about 76%,46%and 42%,respectively.Theoretical calculations further confirm that the Mn vacancies can generate additional occupancy states and cause an increase in carrier concentration,which will improve the conductivity and further boost the pseudocapacitance of MnO_(2).This result open up a promising approach to explore active and durable electrode materials.

Shape-Controlled Synthesis of Platinum-Based Nanocrystals and Their Electrocatalytic Applications in Fuel Cells

To achieve environmentally benign energy conversion with the carbon neutrality target via electrochemical reactions, the innovation of electrocatalysts plays a vital role in the enablement of renewable resources. Nowadays, Pt-based nanocrystals(NCs) have been identified as one class of the most promising candidates to efficiently catalyze both the half-reactions in hydrogen-and hydrocarbonbased fuel cells. Here, we thoroughly discuss the key achievement in developing shape-controlled Pt and Pt-based NCs, and their electrochemical applications in fuel cells. We begin with a mechanistic discussion on how the morphology can be precisely controlled in a colloidal system, followed by highlighting the advanced development of shape-controlled Pt, Pt-alloy, Pt-based core@shell NCs, Pt-based nanocages, and Pt-based intermetallic compounds. We then select some case studies on models of typical reactions(oxygen reduction reaction at the cathode and small molecular oxidation reaction at the anode) that are enhanced by the shape-controlled Pt-based nanocatalysts. Finally, we provide an outlook on the potential challenges of shape-controlled nanocatalysts and envision their perspective with suggestions.

电化学合成耦合可再生能源制氢:机遇与挑战

利用可再生能源实现物质和能量的转化,是发展节能减排技术、实现双碳目标的重要手段.有机电合成是一种温和、清洁、高效的物质合成方法,可以有效解决传统化工过程的高能耗和高污染问题.将电解水制氢与有机电合成耦合,利用水分解产生的活性氧/氢直接氧化/还原有机物,不仅有助于降低能耗,还可以生产高附加值有机化工产品,是提高电能利用效率、降低生产成本的有效方案.然而,尽管这种方法具有诸多优势,其工业化应用仍面临一系列难题.本文回顾了电化学合成的发展历史,探讨了氢能时代为电化学合成带来的发展机遇.同时,分析了将电化学合成与电解水耦合所面临的挑战以及未来发展方向.首先,应当慎重选择与电解水制氢耦合的阳极反应体系,其氧化产物不但要具有比反应物更高的经济价值,而且要有较大的市场需求量,以匹配制氢规模.其次,虽然在热力学上有机物氧化比析氧更容易发生,但在动力学及传质方面,有机物氧化可能存在劣势,因此必须开发适用于工业制氢电流密度(500‒2000 mA cm^(‒2))的有机物氧化电极材料.第三,阳极有机产物选择性不仅影响反应物的利用率,而且决定后续分离纯化成本,需要通过调控活性氢/氧及有机物表面的竞争吸附等手段,提高阳极目标产物选择性及法拉第效率.第四,隔膜是分离两极反应物料、防止副反应发生的重要部件.然而,现有的阴、氧离子交换膜的耐有机物腐蚀性能差,需要开发适用于电解耦合体系的、具有高离子传导能力且性能稳定的新型隔膜材料.最后,当有机物氧化与电解水耦合后,产物的分离复杂程度增加,需要将精馏、萃取、膜分离等手段与电化学反应相结合,以提升电解过程效率.综上,本文讨论了电化学合成耦合可再生能源制氢的若干技术难题,为未来电合成与氢能技术共同发展提供新思路.

Cross-linked polyelectrolyte reinforced SnO_(2)electron transport layer for robust flexible perovskite solar cells

SnO_(2)electron transport layer(ETL)is a vital component in perovskite solar cells(PSCs),due to its excellent photoelectric properties and facile fabrication process.In this study,we synthesized a water-soluble and adhesive polyelectrolyte with ethanolamine(EA)and poly-acrylic acid(PAA).The linear PAA was crosslinked by EA,forming a 3D network that stabilized the SnO_(2)nanoparticle dispersion.An organic–inorganic hybrid ETL is developed by introducing the cross-linked PAA-EA into SnO_(2)ETL,which prevents nano particle agglomeration and facilitates uniform SnO_(2)film formation with fewer defects.Additionally,the PAA-EA-modified SnO_(2)facilitated a uniform and compact perovskite film,enhancing the interface contact and carrier transport.Consequently,the PAA-EA-modified PSCs exhibited excellent PCE of 24.34%and 22.88%with high reproducibility for areas of 0.045 and 1.00 cm~2,respectively.Notably,owing to structure reinforce effect of PAA-EA in SnO_(2)ETL,flexible device demonstrated an impressive PCE of 23.34%while maintaining 90.1%of the initial PCE after 10,000 bending cycles with a bending radius of 5 mm.This successful approach of polyelectrolyte reinforced hybrid organic–inorganic ETL displays great potential for flexible,large-area PSCs application.

Single-frequency linearly polarized Q-switched fiber laser based on Nb_(2)GeTe_(4)saturable absorber

We report a single-frequency linearly polarized Q-switched fiber laser based on an Nb_(2)GeTe_(4)saturable absorber(SA).The Nb_(2)GeTe_(4)SA triggers passive Q-switching of the laser,and an un-pumped Yb-doped fiber together with a 0.08-nmbandwidth polarization-maintaining fiber Bragg grating(FBG)acts as an ultra-narrow bandwidth filter to realize singlelongitudinal-mode(SLM)oscillation.The devices used in the laser are all kept polarized,so as to ensure linearly polarized laser output.Stable SLM linearly polarized Q-switching operation at 1064.6 nm is successfully achieved,producing a laser with a shortest pulse width of 1.36μs,a linewidth of 28.4 MHz,a repetition rate of 28.3 kHz-95.9 kHz,and a polarization extinction ratio of about 30 dB.It is believed that the single-frequency linearly polarized pulsed fiber laser studied in this paper has great application value in gravitational wave detection,beam combining,nonlinear frequency conversion,and other fields.

微波辅助合成促进铬酸铋晶体的光生电荷分离

为了将可再生太阳能转化为化学物质,探索具有宽光谱响应的光催化剂用于光催化分解水越来越受到人们的关注。作为铋基层状金属氧化物的一员,铬酸铋(Bi_(2)CrO_(6))的带隙约为1.9 eV,在利用大范围太阳光谱方面具有潜力。然而,Bi_(2)CrO_(6)较差的电荷分离性能限制了其在光催化中的应用。本文采用微波辅助水热合成方法制备了具有规则形貌的Bi_(2)CrO_(6)晶体,该晶体具有结晶度高、形貌均匀的优点。与传统制备方法相比,微波辐照实现了体系的快速加热,极大地加速了成核和生长的化学反应,从而在几分钟内形成了Bi_(2)CrO_(6)晶体。微波辅助合成的Bi_(2)CrO_(6)晶体在光催化和光电化学测试中表现出更好的光生电荷分离以及水氧化活性。此外实验中观察到光生电子和空穴在Bi_(2)CrO_(6)晶体的不同晶面之间发生空间分离,通过进一步在不同晶面上光沉积选择性负载还原和氧化助催化剂,显著增强了光催化活性。这项工作为制备高效太阳能转换的半导体光催化剂提供了一种可行的解决方案。

Rutin pretreatment promotes microglial M1 to M2 phenotype polarization

Microglial cells are important resident innate immune components in the central nervous system that are often activated during neuroinflammation.Activated microglia can display one of two phenotypes,M1 or M2,which each play distinct roles in neuroinflammation.Rutin,a dietary flavonoid,exhibits protective effects against neuroinflammation.However,whether rutin is able to influence the M1/M2 polarization of microglia remains unclear.In this study,in vitro BV-2 cell models of neuroinflammation were established using 100 ng/mL lipopolysaccharide to investigate the effects of 1-hour rutin pretreatment on microglial polarization.The results revealed that rutin pretreatment reduced the expression of the proinflammatory cytokines tumor necrosis factor-α,interleukin-1β,and interleukin-6 and increased the secretion of interleukin-10.Rutin pretreatment also downregulated the expression of the M1 microglial markers CD86 and inducible nitric oxide synthase and upregulated the expression of the M2 microglial markers arginase 1 and CD206.Rutin pretreatment inhibited the expression of Toll-like receptor 4 and myeloid differentiation factor 88 and blocked the phosphorylation of I kappa B kinase and nuclear factor-kappa B.These results showed that rutin pretreatment may promote the phenotypic switch of microglia M1 to M2 by inhibiting the Toll-like receptor 4/nuclear factor-kappa B signaling pathway to alleviate lipopolysaccharide-induced neuroinflammation.

La and CrCo-doped SrTiO_3 as an H_2 evolution photocatalyst for construction of a Z-scheme overall water splitting system

The photocatalytic activity of a semiconductor‐based photocatalyst largely depends on the semiconductor’s intrinsic crystal and electronic properties.We have prepared two types of La and Cr co‐doped SrTiO3photocatalysts(SrTiO3(La,Cr))using the polymerized complex method(PCM)and sol‐gel hydrothermal method(SHM).Under?>420‐nm visible light irradiation,only the Pt‐loaded SrTiO3(La,Cr)prepared by the SHM showed efficient photocatalytic activities for both H2evolution in the presence of an I?sacrificial reagent and for Z‐scheme overall water splitting when it was coupled with the Pt‐loaded WO3in the presence of I?and IO3?as the shuttle redox mediator.The superior photocatalytic activity of SrTiO3(La,Cr)prepared by the SHM has been ascribed to its more negative conduction‐band position,higher carrier concentration,and higher carrier mobility,demonstrating that the design and synthesis of an H2‐evolution photocatalyst with appropriate electronic properties is crucial for achieving Z‐scheme overall water splitting.

ZnIn_2S_4 flowerlike microspheres embedded with carbon quantum dots for efficient photocatalytic reduction of Cr(Ⅵ)

Development of efficient heterostructured photocatalysts that respond to visible light remains a considerable challenge.We herein show the synthesis of ZnIn2S4/carbon quantum dot hybrid photocatalysts with flowerlike microspheres via a facile solvothermal method.The ZnIn2S4/carbon quantum dot flowerlike microspheres display enhanced photocatalytic and photoelectrochemical activity compared with that of pure ZnIn2S4.With a content of only 0.5 wt%carbon quantum dots,93%of Cr(VI)is reduced under visible‐light irradiation at 40 min.As a co‐catalyst,the carbon quantum dots improve the light absorption and lengthen the lifetime of charge carriers,consequently enhancing the photocatalytic and photoelectrochemical activity.

Single Co atom catalyst stabilized in C/N containing matrix

Single-atom-catalyst （SAC）, which was defined as the active metal site in a catalyst exist as isolated single atoms stabilized by a support or in an alloy by the second coordinate round atoms, is emerging as a new class of heterogeneous catalysts . Compared with nano- and subnano-catalysts, SACs could achieve the atom utilization efficiency up to 100%, offer the opportunities for achieving high activity/selectivity in reac- tions, and bridge the gap between homogeneous and hetero- geneous catalysts. Therefore, SACs may provide a good platform to understand the structure-reactivity relationship at atomic scale.

A Novel Sr_2CuInO_3S p-type semiconductor photocatalyst for hydrogen production under visible light irradiation

A novel Sr2CulnO3S oxysulfide p-type semiconductor photocatalyst has been prepared by solid state reaction method and it exhibits intriguing visible light absorption properties with a bandgap of 2.3 eV. The p-type semiconductor character of the synthesized Sr2CuInO3 S was confirmed by Hall efficient measurement and Mott-Schottky plot analysis. First-principles density functional theory calculations （DFT） and electrochem ical measurements were performed to elucidate the electronic structure and the energy band locations. It was found that the as-synthesized Sr2CuInO3S photocatalyst has appreciate conduction and valence band positions for hydrogen and oxygen evolution, respectively. Photocat alytic hydrogen production experiments under a visible light irradiation （A〉420 nm） were carried out by loading different metal and metal-like cocatalysts on Sr2CuInO3S and Rh was found to be the best one among the tested ones.

Blocking backward reaction on hydrogen evolution cocatalyst in a photosystem Ⅱ hybrid Z-scheme water splitting system

Photocatalytic Z-scheme water splitting is considered as a promising approach to produce solar hydrogen.However,the forward hydrogen production reaction is often impeded by backward reactions.In the present study,in a photosystem Ⅱ-integrated hybrid Z-scheme water splitting system,the backward hydrogen oxidation reaction was significantly suppressed by loading a PtCrOx cocatalyst on a ZrO2/TaON photocatalyst.Due to the weak chemisorption and activation of molecular hydrogen on PtCrOx,where Pt is stabilized in the oxidized forms,Pt^Ⅱ and Pt^Ⅳ,hydrogen oxidation is inhibited.However,it is remarkably well-catalyzed by the metallic Pt cocatalyst,thereby rapidly consuming the produced hydrogen.This work describes an approach to inhibit the backward reaction in the photosystem Ⅱ-integrated hybrid Z-scheme water splitting system using Fe(CN)6^3-/Fe(CN)6^4-redox couple as an electron shuttle.

Tip-induced directional charge separation on one-dimensional BiVO4 nanocones for asymmetric light absorption

One dimensional(1D)semiconductor is a class of extensively attractive materials for many emerging solar energy conversion technologies.However,it is still of shortage to assess the impact of 1D structural symmetry on spatial charge separation and understand its underlying mechanism.Here we take controllably-synthesized 1D BiVO_(4)nanocones and nanorods as prototypes to study the influence of 1D symmetry on charge separation.It is found that the asymmetric BiVO_(4)nanocones enable more effective charge separation compared with the symmetric nanorods.The unexpected spatial charge separation on the nanocones is mainly ascribed to uneven light absorption induced diffusion-controllable charge separation due to symmetry breaking of 1D nanostructure,as evidenced by spatial and temporal resolved spectroscopy.Moreover,the promotion effect of charge separation on the nanocones was quantitatively evaluated to be over 20 times higher than that in BiVO_(4)nanorods.This work gives the first demonstration of the influence of 1D structural symmetry on the charge separation behavior,providing new insights to design and fabricate semiconductor materials for efficient solar energy conversion.

EPR study of charge separation associated states and reversibility of surface bound superoxide radicals in SrTiO_(3) photocatalyst

Understanding the processes of charge generation, transfer and capture is important for the design and synthesis of efficient photocatalysts. In this work, light-induced charge separation and effect of O_(2) on electron transfer processes in SrTiO_(3) were investigated by electron paramagnetic resonance(EPR). It was found that photoinduced electron transfer from O_(2)- to Ti^(4+) produced Ti^(3+) and O- redox radical pairs under vacuum condition. Under oxygen atmosphere, however, surface bound superoxide radicals O_(2)-were formed by electron reduction of adsorbed oxygen at initial photoirradiation stage, and quenched by the reverse electron transfer to Ti^(4+) upon further photoirradiation. Formation of long-lived charge separation associated [Ti^(3+)---O-] species and the reversibility of surface bound superoxide radicals mediating the processes of photogenerated electrons may be accountable for the high activity of SrTiO_(3) in photocatalytic water splitting reaction.

Formation of multifaceted nano-groove structure on rutile TiO_(2) photoanode for efficient electron-hole separation and water splitting

Photoelectrochemical(PEC)water-splitting using solar energy holds great promise for the renewable energy future,and a key challenge in the development of industry viable PEC devices is the unavailability of high-efficient photoanodes.Herein,we designed a TiO_(2) model photocatalyst with nano-groove pattern and different surface orientation using low-energy Ar+irradiation and photoetching of TiO_(2),and significantly improved the intrinsic activity for PEC water oxidation.High-resolution transmission electron microscopy directly manifests that the grooves consist of highly stepped surface with<110>steps and well-crystallized.Transient absorption spectroscopy reveals the groove surface that allows for increased recovery lifetime,which ensures promoted electron-hole separation efficiency.Surface photovoltage directly shows the carrier separation and transportation behaviors,verified by selective photodeposition,demonstrating the groove surface on TiO_(2) contributes to electron-hole separation.This work proposes an efficient and scalable photoanode strategy,which potentially can open new opportunities for achieving efficient PEC water oxidation performance.

Unravelling the essential difference between TiO_(x) and AlO_(x) interface layers on Ta_(3)N_(5) photoanode for photoelectrochemical water oxidation

Tantalum nitride(Ta_(3)N_(5))is a very promising photoanode material due to its narrow band gap(2.1 eV)and suitable band alignment for solar water splitting.However,it suffers from severe photocorrosion during water oxidation.In this work,it was found that surface passivation by AlO_(x) and TiO_(x) layers results in dramatically different PEC performance of Ta_(3)N_(5) photoanode for water oxidation.The mechanism study indicates that the negative charges on AlO_(x) can generate additional field to promote separation of photogenerated charges,while the positive charges on TiO_(x) layer show the opposite effect.As a result,the Ta_(3)N_(5) based photoanode modified with AlO_(x) layer gives a high photocurrent of 12.5 mA cm^(-2) for 24 h at 1.23 V versus the reversible hydrogen electrode(RHE).Dynamic analysis implies that the hole extraction and transfer are significantly improved by the modification with the AlO_(x) layer.This work reveals the importance of the charges on surface passivation layer in interface engineering of photoelectrodes.

Concise Modeling of Amorphous Dual-Gate In-Ga-Zn-O Thin-Film Transistors for Integrated Circuit Designs

An analytical model for current-voltage behavior of amorphous In-Ga-Zn-O thin-film transistors（a-IGZO TFTs）with dual-gate structures is developed.The unified expressions for synchronous and asynchronous operating modes are derived on the basis of channel charges,which are controlled by gate voltage.It is proven that the threshold voltage of asynchronous dual-gate IGZO TFTs is adjusted in proportion to the ratio of top insulating capacitance to the bottom insulating capacitance（C_（TI）/C_（BI））.Incorporating the proposed model with Verilog-A,a touch-sensing circuit using dual-gate structure is investigated by SPICE simulations.Comparison shows that the touch sensitivity is increased by the dual-gate IGZO TFT structure.

Application of near infrared spectroscopy in monitoring the moisture content in freeze-drying process of human coagulation factor VIII

As an important process analysis tool,near infrared spectroscopy(NIRS)has been widely used in process monitoring.In the present work,the feasibility of NIRS for monitoring the moisture content of human coagulation factor VIII(FVIII)in freeze-drying process was investigated.A partial least squares regression(PLS-R)model for moisture content determination was built with 88 samples.Different pre-processing methods were explored,and the best method found was standard normal variate(SNV)transformation combined with 1st derivation with Savitzky–Golay(SG)15 point smoothing.Then,four different variable selection methods,including uninformative variable elimination(UVE),interval partial least squares regression(iPLS),competitive adaptive reweighted sampling(CARS)and manual method,were compared for eliminating irrelevant variables,and iPLS was chosen as the best variable selection method.The correlation coe±cient(R),correlation coe±cient of calibration set(Rcal),correlation coefficient of validation set(Rval),root mean square errors of cross-validation(RMSECV)and root mean square errors of prediction(RMSEP)of PLS model were 0.9284,0.9463,0.8890,0.4986% and 0.4514%,respectively.The results showed that the model for moisture content determination has a wide range,good linearity,accuracy and precision.The developed approach was demonstrated to be a potential for monitoring the moisture content of FVIII in freeze-drying process.

Aromatic bromination with hydrogen production on organic‐inorganic hybrid perovskite‐based photocatalysts under visible light irradiation

Aromatic bromides are important chemicals in nature and chemical industries.However,their tra‐ditional synthesis routes suffer from low atomic economy and pollutant formation.Herein,we show that organic-inorganic hybrid perovskite methylammonium lead bromide(MAPbBr_(3))nanocrystals stabilized in aqueous HBr solution can achieve simultaneous aromatic bromination and hydrogen evolution using HBr as the bromine source under visible light irradiation.By hybridizing MAPbBr_(3) with Pt/Ta_(2)O_(5) and poly(3,4‐ethylenedioxythiophene)polystyrene sulfonate as electron‐and hole‐transporting motifs,aromatic bromides were achieved from aromatic compounds with high yield(up to 99%)and selectivity(up to 99%)with the addition of N,N‐dimethylformamide or its analogs.The mechanistic studies revealed that the bromination proceeds via an electrophilic attack pathway and that HOBr may be the key intermediate in the bromination reaction.

The synthesis of tetracyclic coumarins via decarboxylative asymmetric[4+2]cycloadditions enabled by Pd(0)/Cu(I)synergistic catalysis

Tetracyclic coumarins are a class of important compounds with diverse and superior pharmacolog‐ical activities.However,a direct stereoselective method from simple and readily‐made coumarins derivatives remains challenging due to the inertness of coumarins as dienophiles.Herein,we de‐velop a decarboxylative asymmetric[4+2]cycloaddition of 3‐cyanocoumarins with vinyl benzoxa‐zinones,affording the coumarin‐derived condensed rings bearing three continuous stereocenters in high yields with excellent diastereoselectivities(>20/1 d.r.)and enantioselectivities(up to 99%ee).This direct enantioselective reaction was achieved by a Pd(0)/Cu(I)bimetallic catalytic system.The mechanism studies indicated that the synergistic activation effect,in which chiral Cu(I)as an availa‐ble Lewis acid catalyst activates 3‐cyanocoumarin and chiral Pd(0)complex activates benzoxazi‐none by the formation ofπ‐allyl‐palladium intermediate,plays an important role on the stereoselec‐tive control.The current work provides a new activation modes of Cu catalyst in the Pd/Cu bimetal‐lic catalytic system.