Decouple charge transfer reactions in the Li-ion battery

In the development of Li-ion batteries(LIBs)with high energy/power density,long cycle-life,fast charging,and high safety,an insight into charge transfer reactions is required.Although electrochemical impedance spectroscopy(EIS)is regarded as a powerful diagnosis tool,it is not a direct but an indirect measurement.With respect to this,some critical questions need to be answered:(i)why EIS can reflect the kinetics of charge transfer reactions;(ii)what the inherent logical relationship between impedance models under different physical scenes is;(iii)how charge transfer reactions compete with each other at multiple scales.This work aims at answering these questions via developing a theory framework so as to mitigate the blindness and uncertainty in unveiling charge transfer reactions in LIBs.To systematically answer the above questions,this article is organized into a three-in-one(review,tutorial,and research)type and the following contributions are made:(i)a brief review is given for impedance model development of the LIBs over the past half century;(ii)an open source code toolbox is developed based on the unified impedance model;(iii)the competive mechanisms of charge transfer reactions are unveiled based on the developed EIS-Toolbox@LIB.This work not only clarifies theoretical fundamentals,but also provides an easy-to-use open source code for EIS-Toolbox@LIB to optimize fast charge/discharge,mitigate cycle aging,and improve energy/power density.

Influence of O-O formation pathways and charge transfer mediator on lipid bilayer membrane-like photoanodes for water oxidation

Inspired by the function of crucial components in photosystemⅡ(PSⅡ),electrochemical and dyesensitized photoelectrochemical(DSPEC)water oxidation devices were constructed by the selfassembly of well-designed amphipathic Ru(bda)-based catalysts(bda=2,2'-bipyrdine-6,6'-dicarbonoxyl acid)and aliphatic chain decorated electrode surfaces,forming lipid bilayer membrane(LBM)-like structures.The Ru(bda)catalysts on electrode-supported LBM films demonstrated remarkable water oxidation performance with different O-O formation mechanisms.However,compared to the slow charge transfer process,the O-O formation pathways did not determine the PEC water oxidation efficiency of the dyesensitized photoanodes,and the different reaction rates for similar catalysts with different catalytic paths did not determine the PEC performance of the DSPECs.Instead,charge transfer plays a decisive role in the PEC water oxidation rate.When an indolo[3,2-b]carbazole derivative was introduced between the Ru(bda)catalysts and aliphatic chain-modified photosensitizer in LBM films,serving as a charge transfer mediator for the tyrosine-histidine pair in PSⅡ,the PEC water oxidation performance of the corresponding photoanodes was dramatically enhanced.

Reversed charge transfer induced by nickel in Fe-Ni/Mo_(2)C@nitrogen-doped carbon nanobox for promoted reversible oxygen electrocatalysis

The interaction between metal and support is critical in oxygen catalysis as it governs the charge transfer between these two entities,influences the electronic structures of the supported metal,affects the adsorption energies of reaction intermediates,and ultimately impacts the catalytic performance.In this study,we discovered a unique charge transfer reversal phenomenon in a metal/carbon nanohybrid system.Specifically,electrons were transferred from the metal-based species to N-doped carbon,while the carbon support reciprocally donated electrons to the metal domain upon the introduction of nickel.This led to the exceptional electrocatalytic performances of the resulting Ni-Fe/Mo_(2)C@nitrogen-doped carbon catalyst,with a half-wave potential of 0.91 V towards oxygen reduction reaction(ORR)and a low overpotential of 290 m V at 10 mA cm^(-2)towards oxygen evolution reaction(OER)under alkaline conditions.Additionally,the Fe-Ni/Mo_(2)C@carbon heterojunction catalyst demonstrated high specific capacity(794 mA h g_(Zn)~(-1))and excellent cycling stability(200 h)in a Zn-air battery.Theoretical calculations revealed that Mo_(2)C effectively inhibited charge transfer from Fe to the support,while secondary doping of Ni induced a charge transfer reversal,resulting in electron accumulation in the Fe-Ni alloy region.This local electronic structure modulation significantly reduced energy barriers in the oxygen catalysis process,enhancing the catalytic efficiency of both ORR and OER.Consequently,our findings underscore the potential of manipulating charge transfer reversal between the metal and support as a promising strategy for developing highly-active and durable bi-functional oxygen electrodes.

High-Efficiency Photo-Induced Charge Transfer for SERS Sensing in N-Doped 3D-Graphene on Si Heterojunction

Nitrogen-doped three-dimensional graphene(N-doped 3D-graphene)is a graphene derivative with excellent adsorption capacity,large specific surface area,high porosity,and optoelectronic properties.Herein,N-doped 3D-graphene/Si heterojunctions were grown in situ directly on silicon(Si)substrates via plasma-assisted chemical vapor deposition(PACVD),which is promising for surface-enhanced Raman scattering(SERS)substrates candidates.Combined analyses of theoretical simulation,incorporating N atoms in 3D-graphene are beneficial to increase the electronic state density of the system and enhance the charge transfer between the substrate and the target molecules.The enhancement of the optical and electric fields benefits from the stronger light-matter interaction improved by the natural nano-resonator structure of N-doped 3D-graphene.The as-prepared SERS substrates based on N-doped 3D-graphene/Si heterojunctions achieve ultra-low detection for various molecules:10^(-8)M for methylene blue(MB)and 10^(-9)M for crystal violet(CRV)with rhodamine(R6G)of 10^(10)M.In practical detected,10^(-8)M thiram was precisely detected in apple peel extract.The results indicate that N-doped 3D-graphene/Si heterojunctions based-SERS substrates have promising applications in low-concentration molecular detection and food safety.

First-Principles Investigation of Charge Transfer Mechanism of B-Doped 3C-SiC Semiconductor Material

This study delves into the charge transfer mechanism of boron (B)-doped 3C-SiC through first-principles investigations. We explore the effects of B doping on the electronic properties of 3C-SiC, focusing on a 12.5% impurity concentration. Our comprehensive analysis encompasses structural properties, electronic band structures, and charge density distributions. The optimized lattice constant and band gap energy of 3C-SiC were found to be 4.373 Å and 1.36 eV respectively, which is in agreement with previous research (Bui, 2012;Muchiri et al., 2018). Our results show that B doping narrows the band gap, enhances electrical conductivity, and influences charge transfer interactions. The charge density analysis reveals substantial interactions between B dopants and surrounding carbon atoms. This work not only enhances our understanding of the material’s electronic properties, but also highlights the importance of charge density analysis for characterizing charge transfer mechanisms and their implications in the 3C-SiC semiconductors.

Regulating the interfacial charge transfer and constructing symmetry-breaking sites for the enhanced N_(2) electroreduction activity

The Haber-Bosch process for industrial NH_(3) production is energy-intensive with heavy CO_(2) emissions.Electrochemical N_(2) reduction reaction(NRR)is an attractive carbon-neutral alternative for NH_(3) synthesis,while the challenge associated with N_(2) activation highlights the demand for efficient electrocatalysts.Herein,we demonstrate that PdCu nanoparticles with different Pd/Cu ratios anchored on boron nanosheet(PdCu/B)behave as efficient NRR electrocatalysts toward NH_(3) synthesis.Theoretical and experimental results confirm that the highly efficient NH_(3) synthesis can be achieved by regulating the charge transfer between interfaces and forming a symmetry-breaking site,which not only alleviates the hydrogen evolution but also changes the adsorption configuration of N_(2) and thus optimizes the reaction pathway of NRR over the separated Pd sites.Compared with monometallic Pd/B and Cu/B,the PdCu/B with the optimized Pd/Cu ratio of 1 exhibits superior activity and selectivity for NH_(3) synthesis.This study provides new insight into developing efficient catalysts for small energy molecule catalytic conversion via regulating the charge transfer between interfaces and constructing symmetry-breaking sites.

Regulated adsorption-diffusion and enhanced charge transfer in expanded graphite cohered with N,B bridge-doping carbon patches to boost K-ion storage

The great challenges are remained in constructing graphite-based anode with well built-in structures to accelerate kinetics and enhance stability in the advanced K-ion batteries(KIBs).Here,we firstly report the design of expanded graphite cohered by N,B bridge-doping carbon patches(NBEG)for efficient K-ion adsorption/diffusion and long-term durability.It is the B co-doping that plays a crucial role in maximizing doping-site utilization of N atoms,balancing the adsorption-diffusion kinetics,and promoting the charge transfer between NBEG and K ions.Especially,the robust lamellar structure,suitable interlayer distance,and rich active sites of the designed NBEG favor the rapid ion/electron transfer pathways and high K-ion storage capacity.Consequently,even at a low N,B doping concentration(4.36 at%,2.07 at%),NBEG anode shows prominent electrochemical performance for KIBs,surpassing most of the advanced carbon-based anodes.Kinetic studies,density functional theory simulations,and in-situ Raman spectroscopy are further performed to reveal the K-ion storage mechanism and confirm the critical actions of co-doping B.This work offers the new methods for graphite-electrode design and the deeper insights into their energy storage mechanisms in KIBs.

Design Strategy of Infrared 4-Hydroxybenzylidene-imidazolinone-Type Chromophores based on Intramolecular Charge Transfer:a Theoretical Perspective

Partial genetically encoded 4-hy-droxybenzylidene-imidazolinone(HBI)-type chromophores are new promising fluorescent probes,which are suitable for imaging and detection of living cells.How-ever,the lack of infrared chro-mophores hinders the develop-ment seriously.Here more than 30 HBI-type chromophores with reg-ular structure modifications were employed and typical spectral redshift change laws and mechanisms were investigated by quantum methods.Results show that both one-photon spectrum(OPS,absorption/emission)and two-photon absorption(TPA)can achieve large redshift via either extending conjugated lengths of frag-3 or enlarging conjugated areas of frag-1 of HBI skeleton.Spectral redshifts of all chromophores are highly related to intramolecular charge transfer(ICT),but neutral ones are closely related to the total ICT or electron-accept-ing-numbers of frag-3,and the high correlative factor of anions is the aromaticity of frag-2 bridge.The frag-2 bridge with high aromaticity can open a reverse charge transfer channel in anion relative to neutral,obtaining significant redshift.Based on analysis,a new 6-hydroxyl-naphthalene-imidazolinone(HNI)series,which have larger conjugated area in frag-1,are pre-dicted.The OPS and TPA of anionic HNI ones acquire about 76−96 nm and 119−146 nm red-shift relative to traditional HBI series respectively as a whole.The longest emission of anionic HNI-4 realizes more 244 nm redshift relative to HBI-1.Our work clarifies worthy spectral reg-ularities and redshift mechanisms of HBI-type chromophores and provides valuable design strategy for infrared chromophores synthesis in experiment.

Anomalous photoluminescence enhancement and resonance charge transfer in type-II 2D lateral heterostructures

Type-Ⅱband alignment can realize the efficient charge transfer and separation at the semiconductor heterointerface,which results in photoluminescence(PL)quenching.Recently,several researches demonstrated great enhancement of localized PL at the interface of type-Ⅱtwo-dimensional(2D)heterostructure.However,the dominant physical mechanism of this enhanced PL emission has not been well understood.In this work,we symmetrically study the exciton dynamics of type-Ⅱlateral heterostructures of monolayer MoS_(2) and WS_(2) at room temperatures.The strong PL enhancement along the one-dimensional(1D)heterointerface is associated with the trion emission of the WS_(2) shell,while a dramatic PL quenching of neutral exciton is observed on the MoS_(2) core.The enhanced quantum yield of WS2trion emission can be explained by charge-transfer-enhanced photoexcited carrier dynamics,which is facilitated by resonance hole transfer from MoS_(2) side to WS_(2) side.This work sheds light on the 1D exciton photophysics in lateral heterostructures,which has the potential to lead to new concepts and applications of optoelectronic device.

Incomplete charge transfer in CMOS image sensor caused by Si/SiO_(2)interface states in the TG channel

CMOS image sensors produced by the existing CMOS manufacturing process usually have difficulty achieving complete charge transfer owing to the introduction of potential barriers or Si/SiO_(2)interface state traps in the charge transfer path,which reduces the charge transfer efficiency and image quality.Until now,scholars have only considered mechanisms that limit charge transfer from the perspectives of potential barriers and spill back effect under high illumination condition.However,the existing models have thus far ignored the charge transfer limitation due to Si/SiO_(2)interface state traps in the transfer gate channel,particularly under low illumination.Therefore,this paper proposes,for the first time,an analytical model for quantifying the incomplete charge transfer caused by Si/SiO_(2)interface state traps in the transfer gate channel under low illumination.This model can predict the variation rules of the number of untransferred charges and charge transfer efficiency when the trap energy level follows Gaussian distribution,exponential distribution and measured distribution.The model was verified with technology computer-aided design simulations,and the results showed that the simulation results exhibit the consistency with the proposed model.

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.

Novel CMOS image sensor pixel to improve charge transfer speed and efficiency by overlapping gate and temporary storage diffusing node

A novel CMOS image sensor(CIS) pinned photodiode(PPD) pixel, named as O-T pixel, is proposed and investigated by TCAD simulations. Compared with the conventional PPD pixel, the proposed pixel features the overlapping gate(OG)and the temporary storage diffusing(TSD) region, based on which the several-nanosecond-level charge transfer could be achieved and the complete charge transfer from the PPD to the floating node(FD) could be realized. And systematic analyses of the influence of the doping conditions of the proposed processes, the OG length, and the photodiode length on the transfer performances of the proposed pixel are conducted. Optimized simulation results show that the total charge transfer time could reach about 5.862 ns from the photodiode to the sensed node and the corresponding charge transfer efficiency could reach as high as 99.995% in the proposed pixel with 10 μm long photodiode and 2.22 μm long OG. These results demonstrate a great potential of the proposed pixel in high-speed applications.

Experimental and Theoretical Investigation on Excited State Intramolecular Proton Transfer Coupled Charge Transfer Reaction of Baicalein

The excited state intramolecular proton transfer （ESIPT） coupled charge transfer of baicalein has been investigated using steady-state spectroscopic experiment and quantum chemistry calculations. The absence of the absorption peak from S1 excited state both in the experi-mental and calculated absorption spectra indicates that S1 is a dark state. The dark excited state S1 results in the very weak fluorescence of solid baicalein in the experiment. The fron- tier molecular orbital and the charge difference densities of baicalein show clearly that the S1 state is a charge-transfer state whereas the S2 state is a locally excited state. The only one stationary point on the potential energy profile of excited state suggests that the ESIPT reaction of baicalein is a barrierless process.

Charge transfer in plasma assisted dry reforming of methane using a nanosecond pulsed packed-bed reactor discharge

This paper is aimed to investigate the effect of packing material on plasma characteristic from the viewpoint of charge transfer process.Both the charge accumulation and release processes in the dielectric barrier discharge reactor and packed-bed reactor were investigated by measuring voltage and current waveforms and taking ICCD images.The packing material was ZrO2 pellets and the reactors were driven by a parameterized nanosecond pulse source.The quantity of transferred charges in the dielectric barrier discharge reactor was enhanced when decreasing pulse rise time or increasing pulse width(within 150 ns),but reduced when the gas gap was packed with pellets.The quantity of accumulated charges in the primary discharge was larger than the quantity of released charges in the secondary discharges in the dielectric barrier discharge reactor,but they were almost equal in the packed-bed reactor.It indicates that the discharge behavior has been changed from the view of charge transfer process once the gas gap was packed with pellets,and the ICCD images confirmed it.

Extended Holstein polaron model for charge transfer in dry DNA

The variational method is applied to the study of charge transfer in dry DNA by using an extended Holstein small polaron model in two cases： the site-dependent flnite-chain discrete case and the site-independent continuous one. The treatments in the two cases are proven to be consistent in theory and calculation. Discrete and continuous treatments of Holstein model both can yield a nonlinear equation to describe the charge migration in an actual long-range DNA chain. Our theoretical results of binding energy Eb, probability amplitude of charge carrier Ф and the relation between energy and charge-lattice coupling strength are in accordance with the available experimental results and recent theoretical calculations.

Negative inductive effect enhances charge transfer driving in sulfonic acid functionalized graphitic carbon nitride with efficient visible-light photocatalytic performance

Efficient photogenerated carrier migration/separation plays a critical role in increasing the photocatalytic performance of g-C_(3)N_(4).Herein,sulfonic acid group-functionalized g-C_(3)N_(4)(SACN)was synthesized and then synchronously strengthened by a facile-solid-state thermal reaction of g-C_(3)N_(4)and sulfamic acid.As a solid strong acid,sulfamic acid can be used to achieve acid etching on the surface of g-C_(3)N_(4)with the assistance of thermal treatment,leading to an enlarged specific surface area and increased surface catalytic reaction sites.More importantly,our experiments and density functional theory calculations indicate that the driving force generated by the negative inductive effect of sulfonic acid groups significantly improves the charge transfer dynamics and effectively inhibits their recombination.Moreover,the negative inductive effect can induce charge redistribution,which reduces the conduction band potential of g-C_(3)N_(4)to enhance the reduction ability of photo-induced electrons.As a result,the SACN-400 sample showed excellent photocatalytic performance in H2 generation with an apparent quantum efficiency of 11.03%at 420±15 nm,as well as an efficient photodegradation rate for organic pollutants.

Supplementary Materials: Ultrafast charge transfer in dual graphene-WS_2 van der Waals quadrilayer heterostructures

1. The transient absorption spectra of the WS2 monolayer sample.In the measurement of the transient absorption spectra of the WS2 monolayer sample, A 400-nm (3.1eV) pump pulse with a peak fluence of about 10μJ/cm2excites the electrons from the valence band into the conduction band,the

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.

Significantly enhanced charge transfer efficiency and surface reaction on NiP_(2)/g-C_(3)N_(4) heterojunction for photocatalytic hydrogen evolution

In this work,a novel NiP_(2)/g-C_(3)N_(4)heterojunction via homogeneous precipitation method assisted by thermal phosphorization reaction was designed and constructed,and the optimized sample showed the excellent photocatalytic H_(2)evolution activity under visible-light irradiation,which was nearly 112 times higher than that of pristine g-C_(3)N_(4)sample.Experimental characterizations and DFT calculations demonstrated that the NiP_(2)nanoparticles covered on the g-C_(3)N_(4)surface can form a built-in electric field at the interface to accelerate the transfer of photoexcited electrons from g-C_(3)N_(4)to NiP_(2),crucial for hindering the recombination of electron-hole pairs.Moreover,the energy barrier of hydrogen evolution reaction can also vastly reduce when combined NiP_(2)and g-C_(3)N_(4)to construct NiP_(2)/g-C_(3)N_(4)heterojunction.This work represents a method through combing experimental and theoretical tools to thoroughly investigate the mechanism of photocatalytic process.

Doping-induced charge transfer in conductive polymers

Molecular doping has become a widely used method to modulate the electric performance of organic semiconductors(OSC).Highly effective charge transfer during molecular doping is desired to achieve ideal electrical conductivity.Two types of charge transfer mechanisms are widely accepted in molecular doping process:integer charge transfer(ICT)and charge transfer complex(CTC).In this review,fundamental principles of two mechanisms are revisited and the characterization methods are depicted.The key points for the formation of two mechanisms are highlighted from aspects of molecular structure and process engineering.Then,the strategies to improve the proportion of ICT are discussed.Finally,the challenges and perspectives for future developments in the molecular doping of polymer semiconductors are provided.