Visualization of Metal-to-Ligand and Ligand-to-Ligand Charge Transfer in MetaloLigand Complexes

Three methods including the atomic resolved density of state, charge difference density, and the transition density matrix are used to visualize metal to ligand charge transfer （MLCT） in ruthenium（II） ammine complex. The atomic resolved density of state shows that there is density of Ru on the HOMOs. All the density is localized on the ammine, which reveals that the excited electrons in the Ru complex are delocalized over the ammine ligand. The charge difference density shows that all the holes are localized on the Ru and the electrons on the ammine. The localization explains the MLCT on excitation. The transition density matrix shows that there is electron-hole coherence between Ru and ammine. These methods are also used to examine the MLCT in Os（bpy）2（p0p）Cl （＂Osp0p＂： bpy=2,2-bipyrldyl; p0p=4,4＇- bipyridyl） and the ligand-to-ligand charge transfer （LLCT） in Alq3. The calculated results show that these methods are powerful to examine MLCT and LLCT in the metal-ligand system.

Fast and Balanced Charge Transport Enabled by Solution-Processed Metal Oxide Layers for Efficient and Stable Inverted Perovskite Solar Cells

Metal oxide charge transport materials are preferable for realizing long-term stable and potentially low-cost perovskite solar cells(PSCs).However,due to some technical difficulties(e.g.,intricate fabrication protocols,high-temperature heating process,incompatible solvents,etc.),it is still challenging to achieve efficient and reliable all-metal-oxide-based devices.Here,we developed efficient inverted PSCs(IPSCs)based on solution-processed nickel oxide(NiO_(x))and tin oxide(SnO_(2))nanoparticles,working as hole and electron transport materials respectively,enabling a fast and balanced charge transfer for photogenerated charge carriers.Through further understanding and optimizing the perovskite/metal oxide interfaces,we have realized an outstanding power conversion efficiency(PCE)of 23.5%(the bandgap of the perovskite is 1.62 eV),which is the highest efficiency among IPSCs based on all-metal-oxide charge transport materials.Thanks to these stable metal oxides and improved interface properties,ambient stability(retaining 95%of initial PCE after 1 month),thermal stability(retaining 80%of initial PCE after 2 weeks)and light stability(retaining 90%of initial PCE after 1000 hours aging)of resultant devices are enhanced significantly.In addition,owing to the low-temperature fabrication procedures of the entire device,we have obtained a PCE of over 21%for flexible IPSCs with enhanced operational stability.

Direct Fluorescence Sensing of Metal Ions in Aqueous Solution Using Intramolecular Charge Transfer Emission from Aggregates of Pentaerythrityl Tetra(p-dimethylaminobenzoate)

Pentaerythrityl tetra(p-dimethylaminobenzoate) (PTDMAB) was synthesized and shown to emit in water-rich aqueous dioxane solutions the intramolecular charge transfer fluorescence that was sensitive to the presence of metal ions.

Defect-rich Mg-Al MMOs supported TEPA with enhanced charge transfer for highly efficient and stable direct air capture

Due to the advantages of low energy consumption and high CO_(2) selectivity, the development of solid amine-based materials has been regarded as a hot research topic in the field of DAC for the past decades.The adsorption capacity and stability over multiple cycles have been the top priorities for evaluation of practical application value. Herein, we synthesized a novel DAC material by loading TEPA onto defect-rich Mg_(0.55)Al-O MMOs with enhanced charge transfer effect. The optimal Mg_(0.55)Al-O-TEPA67% demonstrates the highest CO_(2)uptake of(3.0 mmol g^(-1)) and excellent regenerability, maintaining ~90% of the initial adsorption amount after 80 adsorption/desorption cycles. The in situ DRIFTS experiments suggested the formation of bicarbonate species under wet conditions. DFT calculations indicated that the stronger bonding between Mg_(0.55)Al-O support and solid amine was caused by the abundance of oxygen defects on MMOs confirmed by XPS and ESR, which favors the charge transfer between the support and amine,resulting in intense interaction and excellent regenerability. This work for the first time conducted comprehensive and systematic investigation on the stabilization mechanism for MMOs supported solid amine adsorbents with highest uptake and superior cyclic stability in depth, which is different from the most popular SiO_(2)-support, thus providing facile strategy and comprehensive theoretical mechanism support for future research about DAC materials.

Ligand Modified and Light Switched On/Off Single-Chain Magnets of {Fe_(2)Co} Coordination Polymers via Metal-to-Metal Charge Transfer

It is still a formidable challenge to simultaneously switch single-chain magnet(SCM)behavior via ligand modification and light irradiation in the field of molecular spintronics.Herein,we present a ligandbridged layer{[pzTpFe(CN)3]4Co2(Bib)4}·3H2O(1;pzTp,tetra-kis(1-pyrazolyl)borate;Bib,1,4-bis-(1Himidazol-1-yl)benzene)and a well-isolated double chain{[pzTpFe(CN)3]2Co(Bpi)2}·CH3CN·4H2O(2;Bpi,1-Biphenyl-4-yl-1H-imidazole)that display reversible metal-to-metal charge transfer(MMCT)between FeIII LS(μ-CN)CoII HS(μ-NC)FeIII LS(LS,low spin;HS,high spin)and FeIII LS(μ-CN)CoIII LS(μ-NC)FeII LS linkages under alternating irradiation with 808 and 532 nm lasers.The bidirectional light irradiations induces significant changes in anisotropy and intrachain magnetic interactions,resulting in the on/off switching of SCM behavior with observable hysteresis loops by 808 and 532 nm light irradiations for both compounds.Because of the ligand modification,the SCM property of 2 with the monodentate ligand is greatly improved with a correlation length increased to 83,which is the largest correlation length among all reported light actuated SCMs.Furthermore,the influence of ligand modification on their thermally induced MMCT is also discussed.This study provides a rational approach for the swift and reversible control of SCM behavior via ligand modified and light induced MMCT,which is crucial to the future technological demand for high-density data storage and processing.

Rationally construction of atomic-precise interfacial charge transfer channel and strong build-in electric field in nanocluster-based Zscheme heterojunctions with enhanced photocatalytic hydrogen production

The lack of effective charge transfer driving force and channel limits the electron directional migration in nanoclusters(NC)-based heterostructures,resulting in poor photocatalytic performance.Herein,a Z-scheme NC-based heterojunction(Pt1Ag28-BTT/CoP,BTT=1,3,5-benzenetrithiol)with strong internal electric field is constructed via interfacial Co-S bond,which exhibits an absolutely superiority in photocatalytic performance with 24.89 mmol·h^(−1)·g−1 H_(2)production rate,25.77%apparent quantum yield at 420 nm,and~100%activity retention in stability,compared with Pt1Ag28-BDT/CoP(BDT=1,3-benzenedithiol),Ag29-BDT/CoP,and CoP.The enhanced catalytic performance is contributed by the dual modulation strategy of inner core and outer shell of NC,wherein,the center Pt single atom doping regulates the band structure of NC to match well with CoP,builds internal electric field,and then drives photogenerated electrons steering;the accurate surface S modification promotes the formation of Co-S atomic-precise interface channel for further high-efficient Z-scheme charge directional migration.This work opens a new avenue for designing NC-based heterojunction with matchable band structure and valid interfacial charge transfer.

New insights into “dead lithium” during stripping in lithium metal batteries

Lithium (Li) metal attributes to the promising anode but endures the low Columbic efficiency (CE) and safety issues from the inactive Li accumulation. The metallic Li which is isolated from the lithium anode (named dead Li^(0)) consists the major component of the inactive Li. We systematically and meticulously investigated the formation and evaluation of dead Li^(0) during stripping process from electron transfer, the oxidation of Li^(0) to Li^(+) and the diffusion of Li^(+) through solid electrolyte interphase (SEI). The above-mentioned processes were regulated by adjusting the contact sites of electron channels, the dynamic rate of conversion from Li^(0) to Li^(+), and the structure as well as components of SEI. The design principles for achieving less dead Li^(0) and higher CE are proposed as a proof of concept in lithium metal batteries. This new insight sheds a comprehensive light on dead Li^(0) formation and guides the next-generation safe batteries for future application.

A comparison study of alkali metal-doped g-C_3N_4 for visible-light photocatalytic hydrogen evolution

Photocatalytic hydrogen production based on semiconductor photocatalysts has been considered as one of the most promising strategies to resolve the global energy shortage.Graphitic carbon nitride(g‐C3N4)has been a star visible‐light photocatalyst in this field due to its various advantages.However,pristine g‐C3N4usually exhibits limited activity.Herein,to enhance the performance of g‐C3N4,alkali metal ion(Li+,Na+,or K+)‐doped g‐C3N4are prepared via facile high‐temperature treatment.The prepared samples are characterized and analyzed using the technique of XRD,ICP‐AES,SEM,UV‐vis DRS,BET,XPS,PL,TRPL,photoelectrochemical measurements,photocatalytic tests,etc.The resultant doped photocatalysts show enhanced visible‐light photocatalytic activities for hydrogen production,benefiting from the increased specific surface areas(which provide more active sites),decreased band gaps for extended visible‐light absorption,and improved electronic structures for efficient charge transfer.In particular,because of the optimal tuning of both microstructure and electronic structure,the Na‐doped g‐C3N4shows the most effective utilization of photogenerated electrons during the water reduction process.As a result,the highest photocatalytic performance is achieved over the Na‐doped g‐C3N4photocatalyst(18.7?mol/h),3.7times that of pristine g‐C3N4(5.0?mol/h).This work gives a systematic study for the understanding of doping effect of alkali metals in semiconductor photocatalysis.

Efficient quasi-stationary charge transfer from quantum dots to acceptors physically-adsorbed in the ligand monolayer

Alkanoate-coated CdSe/CdS core/shell quantum dots(QDs)with near-unity photoluminescence(PL)quantum yield and monoexponential PL decay dynamics are applied for studying quasi-stationary charge transfer from photo-excited QDs to quinone derivatives physically-adsorbed within the ligand monolayer of a QD.Though PL quenching efficiency due to electron transfer can be up to>80%,transient PL and transient absorption spectra reveal that the charge transfer rate ranges from single-digit nanoseconds to sub-nanoseconds,which is~3 orders of magnitude slower than that of static charge transfer and〜2 orders of magnitude faster than that of collisional charge transfer.The physically-adsorbed acceptors can slowly(500-1,000 min dependent on the size of the quinone derivatives)desorb from the ligand monolayer after removal of the free acceptors.Contrary to collisional charge transfer,the efficiency of quasi-stationary charge transfer increases as the ligand length increases by providing additional adsorption compartments in the elongated hydrocarbon chain region.Because ligand monolayer commonly exists for a typical colloidal nanocrystal,the quasi-stationary charge transfer uncovered here would likely play an important role when colloidal nanocrystals are involved in photocatalysis,photovoltaic devices,and other applications related to photo-excitation.

Coupling metal oxide nanoparticle catalysts for water oxidation to molecular light absorbers

Water oxidation, as a mandatory reaction of solar fuels conversion systems, requires the use of light absorbers with electronic properties that are well matched with those of the multi-electron catalyst in order to achieve high efficiency. Molecular light absorbers offer flexibility in fine tuning of orbital energetics,and metal oxide nanoparticles have emerged as robust oxygen evolving catalysts. Hence, these material choices offer a promising approach for the development of photocatalytic systems for water oxidation.However, efficient charge transfer coupling of molecular light absorbers and metal oxide nanoparticle catalysts has proven a challenge. Recent new approaches toward the efficient coupling of these components based on synthetic design improvements combined with direct spectroscopic observation and kinetic evaluation of charge transfer processes are discussed.

Theoretical Investigation of Nonlinear Optical Properties of Organicand Transition Metal Hybrid Azobenzene Dendrimers

In this work, we report a theoretical exploration of the responses of organic azobenzene dendrimers. The polarizabilities, the first and second hyperpolarizabilities of the azobenzene monomers （GO）, and the first, second and third generation （G1, G2 and G3, respectively） are investigated by semi-empirical methods. The calculated results show that the nonlinear optical （NLO） properties of these organic dendrimers are mainly determined by the azobenzene chromospheres. Additionally, the values oft and y increase almost in proportion to the number of chromophores. On the other hand, two types of transition metal hybrid azobenzene dendrimers （core-hybrid and branch-end hybrid according to the sites combined with transition metals） are simulated and discussed in detail in the framework of time-dependent density functional theory （TDDFT）. The calculated results reveal that the NLO responses of these metal dendrimers distinctly varied as a result of altering the charge transfer transition scale and the excitation energies.

First-principles study of electronic properties of interfacial atoms in metal-metal contact electrification

The mechanism of contact electrification between metals was studied using the first-principles method, taking the Ag-Fe contact as an example. Charge population, charge density difference, the orbitals and densities of states （DOS） were calculated to study the electronic properties of the contacting interfacial atoms. Based on the calculation, the amount of contact charge was obtained. The investigation revealed that the electrons near Fermi levels with higher energies transfer between the outermost orbitals （s orbitals for Ag and d orbitals for Fe）. Meanwhile, polarized covalent bonds form between the d electrons in the deep energy states. These two effects together lead to an increase of charge magnitude at the interface. Also, the electrons responsible for electrification can be determined by their energies and orbitals.

配体-金属电子转移强化类芬顿技术的破络特性与机制

为有效分解近中性废水中典型难降解强络合物Ni-EDTA,构建配体-金属电子转移强化类芬顿技术(LFGR),基于Ni(Ⅱ)去除效能等系统分析其在近中性条件下对Ni-EDTA的破络特性,重点探究Fe(Ⅲ)与H2O2投加量、pH值、浊度、常见有机酸与常规无机盐对LFGR破络特性的影响。结合H2O2消耗观测、自由基淬灭实验、自由基信号检测与降解产物分析等科学识别LFGR体系中主要活性氧物种,并进一步剖析Ni-EDTA的破络过程与主导机制。定量比较分析LFGR与其他UV活化氧化技术去除多种重金属EDTA络合物(M-EDTA)的特性,并进一步阐明LFGR的运行成本优势。对于络合物浓度为1.0 mmol/L的近中性模拟废水,LFGR的优化反应条件为:Fe(Ⅲ)投加量为0.1 mmol/L,H2O2投加量为50 mmol/L,UV光照时间为20 min。该条件下,EDTA可完全转化,且经碱沉淀后Ni(Ⅱ)去除率可高达99.40%;LFGR对水中常见有机酸与常规无机盐呈现出良好的抗干扰性;H_(2)O_(2)主要通过与配体-金属电子转移产生的Fe(Ⅱ)发生类芬顿反应消耗;LFGR的主要作用过程是Fe(Ⅲ)置换Ni(Ⅱ)并激发配体-金属电子转移反应从而促进EDTA光解,UV进一步驱动Fe(Ⅲ)还原并加快Fe物种循环,进而强化类芬顿技术活性氧自由基(主要为·OH和·O_(2)^(-))的催化作用。LFGR可在近中性条件下实现多种M-EDTA的良好破络效果,水处理费用合计为4.21元/t,具有良好技术经济性。

Mn^(2+)掺杂准二维钙钛矿(PEA)_(2)Pb_(y)Mn_(1-y)Br_(4)的制备及其电致发光性能

制备了具有高荧光量子产率(photoluminescence quantum yield,PLQY)的Mn^(2+)掺杂准二维钙钛矿(PEA)_(2)Pb_(y)Mn_(1-y)Br_(4)(PEA为苯乙胺,y为Pb^(2+)占Mn^(2+)和Pb^(2+)总含量的物质的量分数)薄膜。宽带隙的(PEA)_(2)PbBr_(4)作为给体,掺杂杂质Mn^(2+)作为受体,构筑了双发射的激发态传递系统。通过调控Mn^(2+)掺杂的不同比例对(PEA)_(2)Pb_(y)Mn_(1-y)Br_(4)的发光性能和薄膜形貌的影响,发现当前驱体溶液中Mn^(2+)与Pb^(2+)的物质的量之比为1∶4时,薄膜有着最高的PLQY和最低的表面粗糙度。利用飞秒瞬态吸收(transient absorption,TA)光谱,追踪其动力学过程,发现主客体之间的激发态传递是通过电荷转移来实现的。为了研究材料的电致发光特性,我们将(PEA)_(2)Pb_(y)Mn_(1-y)Br_(4)作为活性层,加工得到了发光二极管(light emitting diodes,LEDs)。在室温下,器件发出明亮的橙色,其最高的发光强度为0.21 cd·m^(-2),外量子效率(external quantum efficiency,EQE)为0.0025%。

Heterostructures of Ni(II)-doped CdS quantum dots andβ-Pb_(0.33)V_(2)O_(5)nanowires:Enhanced charge separation and redox photocatalysis via doping of QDs

We synthesized heterostructures by tethering Ni(II)-doped CdS(Ni:CdS)quantum dots(QDs)toβ-Pb_(0.33)V_(2)O_(5)nanowires(NWs)using L-cysteine as a molecular linker,and we evaluated the influence of doping on their redox photocatalytic reactivity.We initially hypothesized that incorporating Ni:CdS QDs into heterostructures could alter excited-state dynamics and mechanisms,and that the localization of excited electrons on Ni 3d states could promote redox photocatalytic mechanisms including reduction of CO_(2).Isolated Ni:CdS QDs were ferromagnetic,and they exhibited enhanced photocatalytic hydrogen evolution and photostability relative to undoped CdS QDs.Both Pb_(0.33)V_(2)O_(5)/CdS heterostructures(with undoped QDs)and Pb_(0.33)V_(2)O_(5)/Ni:CdS heterostructures(with Ni(II)-doped QDs)exhibited substantial energetic overlap between valence-band states of QDs and intercalative mid-gap states ofβ-Pb_(0.33)V_(2)O_(5)NWs.Within Pb_(0.33)V_(2)O_(5)/CdS heterostructures,photoexcitation of CdS QDs was followed by rapid(50-100 ps)transfer of both holes and electrons toβ-Pb_(0.33)V_(2)O_(5)NWs.In contrast,within Pb_(0.33)V_(2)O_(5)/Ni:CdS heterostructures,holes were transferred from Ni:CdS QDs toβ-Pb_(0.33)V_(2)O_(5)NWs within 100 ps,but electrons were transferred approximately 20-fold more slowly.This difference in electron-and hole-transfer kinetics promoted charge separation across the Pb_(0.33)V_(2)O_(5)/Ni:CdS interface and enabled the photocatalytic reduction of CO_(2)to CO,CH_(4),and HCO_(2)H with>99.9%selectivity relative to the reduction of H+to H2.These results highlight the opportunity to fine-tune dynamics and mechanisms of excitedstate charge-transfer,and mechanisms of subsequent redox half-reactions,by doping QDs within heterostructures.Moreover,they reveal the promise of heterostructures comprising QDs and MxVyO5 materials as CO_(2)-reduction photocatalysts.

Interfacial compatibility issues in rechargeable solid-state lithium metal batteries:a review

Solid-state lithium metal batteries(SSLBs)contain various kinds of interfaces,among which the solid electrode|solid electrolyte(ED|SE)interface plays a decisive role in the battery's power density and cycling stability.However,it is still lack of comprehensive knowledge and understanding about various interfacial physical/chemical processes so far.Although tremendous efforts have been dedicated to investigate the origin of large interfacial resistance and sluggish charge(electron/ion)transfer process,many scientific and technological challenges still remain to be clarified.In this review,we detach and discuss the critical individual challenge,including charge transfer process,chemical and electrochemical instability,space charge layers,physical contact and mechanical instability.The fundamental concepts,individual effects on the charge transfer and potential solutions are summarized based on material's thermodynamics,electrode kinetics and mechanical effects.It is anticipated that future research should focus on quantitative analysis,modeling analysis and in-situ microstructure characterizations in order to obtain an efficient manipulation about the complex interfacial behaviors in all solid-state Li batteries.

Sandwich-type composited solid polymer electrolytes to strengthen the interfacial ionic transportation and bulk conductivity for all-solid-state lithium batteries from room temperature to 120℃

The insurmountable charge transfer impedance at the Li metal/solid polymer electrolytes(SPEs)interface at room temperature as well as the ascending risk of short circuits at the operating temperature higher than the melting point,dominantly limits their applications in solid-state batteries(SSBs).Although the inorganic filler such as CeO_(2)nanoparticle content of composite solid polymer electrolytes(CSPEs)can significantly reduce the enormous charge transfer impedance at the Li metal/SPEs interface,we found that the required content of CeO_(2)nanoparticles in SPEs varies for achieving a decent interfacial charge transfer impedance and the bulk ionic conductivity in CSPEs.In this regard,a sandwich-type composited solid polymer electrolyte with a 10%CeO_(2)CSPEs interlayer sandwiched between two 50%CeO_(2)CSPEs thin layers(sandwiched CSPEs)is constructed to simultaneously achieve low charge transfer impedance and superior ionic conductivity at 30℃.The sandwiched CSPEs allow for stable cycling of Li plating and stripping for 1000 h with 129 mV polarized voltage at 0.1 mA cm^(-2)and 30℃.In addition,the LiFePO_(4)/Sandwiched CSPEs/Li cell also exhibits exceptional cycle performance at 30℃and even elevated120℃without short circuits.Constructing multi-layered CSPEs with optimized contents of the inorganic fillers can be an efficient method for developing all solid-state PEO-based batteries with high performance at a wide range of temperatures.

Construction of high-efficiency CoS@Nb_(2)O_(5) heterojunctions accelerating charge transfer for boosting photocatalytic hydrogen evolution

The random movement and easy recombination of photoinduced charges lead to a low conversion efficiency for photocatalytic hydrogen evolution.The cocatalyst design is a promising route to address such problem through introducing an appropriate cocatalyst on the semiconductor photocatalysts to construct the high-efficiency heterojunctions.Herein,novel CoS/Nb_(2)O_(5) heterojunctions were constructed via in-situ loading CoS cocatalyst on the surface of Nb_(2)O_(5) nanosheets.Through the femtosecond-resolved transient absorption spectroscopy,the average lifetime of charge carriers for 10 wt% CoS/Nb_(2)O_(5)(159.6 ps)is drastically shortened by contrast with that of Nb_(2)O_(5)(5531.9 ps),strongly suggesting the rapid charge transfer from Nb_(2)O_(5) to CoS.The significantly improved charge-transfer capacity contributes to a high photocatalytic hydrogen evolution rate of 355µmol/h,up to 17.5 times compared with pristine Nb_(2)O_(5).This work would provide a new design platform in the construction of photocatalytic heterojunctions with high charge-transfer efficiency.

Structure, charge transfer, and superconductivity of M-doped phenanthrene(M = Al, Ga, and In): A comparative study of K-doped cases

Aromatic hydrocarbons doped with K have been shown to be potential high-temperature superconductors. To investigate the doping effects of trivalent metals(Al, Ga, and In) that have a smaller radii than K, we studied the crystal structure, stability,charge transfer, band structure, and superconductivity of trivalent metal-doped phenanthrene via first-principles calculations.Doping with Al/Ga/In considerably differs from doping with K and cannot be simply regarded as a linear developmental change in the structural and electronic characteristics caused by a change in the valence electron numbers. Al/Ga/In atoms are difficult to dope into the intralayer region, and the charge transfer is close to zero, which is far less than the effect of K doping. We found that the metallization of the Al/Ga/In-doped system originates from the formation of gap states instead of charge transfer. The weak superconductivity obtained in the Al/Ga/In-doped system is also different from the K-doped system. These results are helpful in terms of understanding the structure and superconductivity of metal-doped aromatic superconductors.

二氰基二硫纶·邻菲咯啉合钴（Ⅱ）掺杂CdS的光电导和光敏性研究

测量了掺杂有标题配合物ＣｏＬＬ＇（Ｌ＝ｍｎｔ２－；Ｌ＇＝ｐｈｅｎ，５－ＮＯ２－ｐｈｅｎ）的ＣｄＳ－ＰＶＡ复合膜的暗态导电性和光电导性以及该类配合物ＣｏＬＬ＇在ＤＭＦ中的电子吸收光谱和发射光谱，研究了ＣｏＬＬ＇对ＣｄＳ的光敏化作用与其电子光谱间的关系。结果表明，ＣｏＬＬ＇的配体间荷移跃迁能量与ＣｄＳ的禁带宽度（或光导红限）存在明显的匹配性。