Defect engineering in transition-metal(Fe,Co,andNi)-based electrocatalysts for water splitting

Electrocatalytic water splitting seems to be an efficient strategy to deal with increasingly serious environmental problems and energy crises but still suffers from the lack of stable and efficient electrocatalysts.Designing practical electrocatalysts by introducing defect engineering,such as hybrid structure,surface vacancies,functional modification,and structural distortions,is proven to be a dependable solution for fabricating electrocatalysts with high catalytic activities,robust stability,and good practicability.This review is an overview of some relevant reports about the effects of defect engineering on the electrocatalytic water splitting performance of electrocatalysts.In detail,the types of defects,the preparation and characterization methods,and catalytic performances of electrocatalysts are presented,emphasizing the effects of the introduced defects on the electronic structures of electrocatalysts and the optimization of the intermediates'adsorption energy throughout the review.Finally,the existing challenges and personal perspectives of possible strategies for enhancing the catalytic performances of electrocatalysts are proposed.An in-depth understanding of the effects of defect engineering on the catalytic performance of electrocatalysts will light the way to design high-efficiency electrocatalysts for water splitting and other possible applications.

Two positive effects with one arrow:Modulating crystal and interfacial decoration towards high-potential cathode material

As the primary suppliers of cyclable sodium ions,O3-type layer-structured manganese-based oxides are recognized as highly competitive cathode candidates for sodium-ion batteries.To advance the development of high-energy sodium-ion batteries,it is crucial to explore cathode materials operating at high voltages while maintaining a stable cycling behavior.The orbital and electronic structure of the octahedral center metal element plays a crucial role in maintaining the octahedra structural integrity and improving Na^(+)ion diffusion by introducing heterogeneous chemical bonding.Inspired by the abundant configuration of extra nuclear electrons and large ion radius,we employed trace amounts of tungsten in this study.The obtained cathode material can promote the reversibility of oxygen redox reactions in the high-voltage region and inhibit the loss of lattice oxygen.Additionally,the formation of a Na_(2)WO_(4) coating on the material surface can improve the interfacial stability and interface ions diffusion.It demonstrates an initial Coulombic efficiency(ICE)of 94.6%along with 168.5 mA h g^(-1 )discharge capacity within the voltage range of 1.9-4.35 V.These findings contribute to the advancement of high-energy sodium-ion batteries by providing insights into the benefits of tungsten doping and Na_(2)WO_(4) coating on cathode materials.

Appreciable Enhancement of Photocatalytic Performance for N-doped SrMoO_(4) via the Vapor-thermal Method

A series of nitrogen-doped SrMoO_(4) with different Sr/N mole ratio (R=0,0.05,0.10,0.15,0.20,0.40,and 0.60) were synthesized using urea as the N source via the vapor-thermal method.The photocatalytic degradation ability of all samples was evaluated using methylene blue (MB) as a target contaminant.The band gaps of N-doped samples are all higher than that of pristine ones,which is only 3.12 eV.BET specific surface area S_(BET) and pore volume are increased due to the N doping.And the greater increase of S_(BET),the faster the photodegradation speed of methylene blue on SrMoO_(4).More specifically,the degradation efficiency of MB is improved up to 87%in 100 min.

Influence of Doped Elements on Electrochemical High Temperature Performance of La-riched Hydrogen Storage Material

The effects of small amounts of added elements such as aluminum, titanium and zirconium to MlNi 3.8(CoMn) 1.2 on its electrochemical performances and performances at high temperatures were investigated.It is found that the addition of aluminum brings about a significant increase in the discharge capacity at high temperatures,and the capacity decay during repeated charge-discharge cycles and the self-discharge are both suppressed, while the rate capability decreases.The alloy containing zirconium exhibits a longer cycle life and a better rate capability,but a much lower discharge capacity.The addition of titanium improves the rate capability, but the capacity decreases greatly.An X-ray diffraction analysis indicates that a second phase exists in the alloy with additive Zr or Ti,which improves the discharge-rate characteristics,and the superior stability of the alloy with additive Al may be due to the expansion of lattice parameters and cell volume.

Infrared emissivity of transition elements doped ZnO

Infrared emissivity was studied in Zno.99Mo.olO （M is Mn, Fe or Ni） and Znl_xCoxO （x=0.01, 0.02, 0.03 and 0.04） powders synthesized by solid-state reaction at various temperatures. XRD patterns confirm the wurtzite structure of the prepared samples. No peaks of other phases arising from impurities are detected in Mn- and Co-doped ZnO, hut the peaks of ZnFe204 and NiO are observed in Zno.99Feo.010 and Zno.99Nio.o10. The SEM observations indicate that with larger grain sizes than those of Zn0.99Feo.010 and Zno.99Ni0.010, Co-doped ZnO exhibits smooth grain surfaces. The infrared absorption spectra show that infrared absorptions related to oxygen in Zn0.99M0.010 are much stronger than those in Co-doped ZnO. Co ions are dissolved into the ZnO lattice with Co2＋ state from XPS spectra analysis. The infrared emissivity results imply that the emissivity of Zno.99Ni0.010 is the highest （0.829） and that of Zno.99C00.010 is the lowest （0.784） at 1 200 ℃. The emissivity of Zno.99Co0.010 decreases to the minimum （0.752） at 1 150 ℃ and then increases with growing calcination temperature. As the Co doping content grows, the emissivity of Co-doped ZnO calcined at 1 200 ℃ falls to 0.758 in the molar fraction of 3% and then ascends.

The Influence of Alkaline Earth Elements on Electronic Properties ofα-Si3N4 via DFT Calculation

We used density functional theory(DFT)calculations to study the influence of alkali earth metal element(AE)doping on the crystal structure and electronic band structure ofα-Si3N4.The diversity of atomic radii of alkaline earth metal elements results in structural expansion when they were doped into theα-Si3N4 lattice.Formation energies of the doped structures indicate that dopants prefer to occupy the interstitial site under the nitrogen-deficient environment,while substitute Si under the nitrogen-rich environment,which provides a guide to synthesizingα-Si3N4 with different doping types by controlling nitrogen conditions.For electronic structures,energy levels of the dopants appear in the bottom of the conduction band or the top of the valence band or the forbidden band,which reduces the bandgap ofα-Si3N4.

Elemental Doping Boosts Charge-Transfer Excitonic States in Polymeric Photocatalysts for Selective Oxidation Reaction

Energy-transfer-mediated synthetic reactions play vital roles in the production of high-value-added organics,where the longlived exciton harvesting is an essential precondition for the process.However,for semiconductors with strong excitonic effects like conjugated polymers,their predominant Frenkel exciton with a short lifetime in the unified framework gives rise to low efficiency photocatalysis.Herein,we propose the boosting of the charge-transfer exciton with a long-lived state by introducing spatially separated electron and hole regions.By taking polymeric carbon nitride(PCN)as a prototype,we demonstrate that sulfur doping leads to the formation of electron donor and acceptor motifs in the tri-s-triazinebased backbone,which would accommodate long-lived excitonic states with remarkable charge-transfer characteristics.The extraordinary long-lived charge-transfer exciton harvesting endows sulfur-doped PCN with high-efficiency photocatalytic performance in 1O2 generation and selective oxidation of organic sulfides.This work provides a brand new perspective for designing advanced photocatalysts for energy-transfer-mediated sunlight utilization.

Electronic modulation of sprout-shaped NiCoP nanoarrays by N and Ce doping for efficient overall water splitting

Bifunctional catalysts for hydrogen/oxygen evolution reactions(HER/OER)are urgently needed given the bright future of water splitting hydrogen production technology.Here,the self-supporting N and Ce dual-doped NiCoP nanoarrays(denoted N,Ce-NiCoP/NF)grown on Ni foam are successfully constructed.When the N,Ce-NiCoP/NF simultaneously acts as the HER and OER electrodes,the voltages of 1.54 and 2.14 V are obtained for driving 10 and 500 mA·cm^(-2)with a robust durability,and demonstrate its significant potential for practical water electrolysis.According to both experiments and calculations,the electronic structure of NiCoP may be significantly altered by strategically incorporating N and Ce into the lattice,which in turn optimizes the Gibbs free energy of HER/OER intermediates and speeds up the water splitting kinetics.Moreover,the sprout-shaped morphology significantly increases the exposure of active sites and facilitates charge/mass transfer,thereby augmenting catalyst performance.This study offers a potentially effective approach involving the regulation of anion and cation double doping,as well as architectural engineering,for the purpose of designing and optimizing innovative electrocatalysts.

Fluorescence and cofluorescence enhancement of Tb(Ⅲ) complexes with pyromellitic acid by M (M = Gd, La, Ca, and Sr ions)

Fluorescence and cofluorescence properties of Tb(Ⅲ) solid complexes werestudied using pyromellitic acid (PMA) as ligand and fluorescence inert ions as doping elements. Thecofluorescence enhancement, a result of ligand sensitized fluorescence, was observed in Tb(Ⅲ) solidcomplexes doped with fluorescent inert ions La(Ⅲ), Gd(Ⅲ), Ca(Ⅲ), and Sr(Ⅲ). The effect of thetype and content of doping elements on fluorescence enhancement was studied, and optimum conditionswere determined. The results show that Gd (La, Ca, Sr) has clear cofluorescence effect in solidcomplex Tb-M-PMA system, and in present work, rare earth complex fluorescent powder that emitsbright green fluorescence at ultraviolet excitation was obtained, which had potential application asfluorescent anti-counterfeit ink.

Modified g-C_(3)N_(4) derived from ionic liquid and urea for promoting visible-light photodegradation of organic pollutants

In this work,modified g-C_(3)N_(4) was fabricated successfully by calcination of ionic liquid(IL) and urea.The addition of IL changed the polymerization mode of urea,induced the self-assembly of urea molecules,modified the morphological structure of the tightly packed g-C_(3)N_(4),and extended the electron conjugation system.When using 1-butyl-3-methylimidazolium chloride([Bmim]Cl) as a modifier,the heteroatom Cl could be inserted into the g-C_(3)N_(4) to optimize the electronic structure.The results of characterizations indicate that the unique structure of modified g-C_(3)N_(4) has an expanded electron delocalization range,introduces an interlayer charge transmission channel,promotes the charge transmission,reduces the band gap,enhances the absorption of visible light,and inhibits electron-hole recombination.Modified g-C_(3)N_(4) showed excellent photocatalytic performance for the degradation of rhodamine B and tetracycline.Furthermore,the effect of different anions in 1-butyl-3-methylimidazolium salts([Bmim]Cl,[Bmim]Br,[Bmim][BF_(4)],and [Bmim][PF_6]) on the structure and function of g-C_(3) N_(4) are discussed.

Transition metal carbonate anodes for Li-ion battery: fundamentals,synthesis and modification

Even though transition metal carbonates(TMCs, TM = Fe, Mn, Co, Ni etc.), show high theoretical capacities, rich reserves and environmental friendliness as anodes for lithium-ion batteries(LIBs), they suffer from sluggish electronic/ionic conductivities and huge volume variation, which severely deteriorate the rate capacities and cycling performances. Understanding the intrinsic reaction mechanism and further developing ideal TMC-based anode with high specific capacity, excellent rate capabilities, and longterm cycling stability are critical for the practical application of TMCs. In this review, we firstly focus on the fundamental electrochemical energy-storage mechanisms of TMCs, in terms of conversionreaction process, pseudocapacitance-type charge storage, valence change for charge storage and catalytic conversion mechanisms. Based on the reaction mechanisms, various modification strategies to improve the electrochemical performance of TMCs are summarized, covering:(i) micro-nano structural engineering, in which the influence factors on the morphology are discussed, and multiple architectures are listed;(ii) elemental doping, in which the intrinsic mechanisms of metal/nonmetal elements doping on the electrochemical performance are deeply explored;(iii) multifunctional compositing strategies, in which the specific affections on structure, electronic conductivity and chemo-mechanical stability are summarized.Finally, the key challenges and opportunities to develop high-performance TMCs are discussed and some solutions are also proposed. This timely review sheds light on the path towards achieving cost-effective and safe LIBs with high energy density and long cycling life using TMCs-based anode materials.

A Fundamental DFT Study of Anatase(TiO2) Doped with 3d Transition Metals for High Photocatalytic Activities

Anatase（TiO_2） has been widely used in photocatalysis. However, it can only absorb near-ultraviolet light with a wavelength below approximately 388 nm due to a wide band gap. Therefore a modification should be made for anatase to increase its capability in utilizing more abundant visible light. We investigated the doped anatase with the most promising 3d transition metal elements, and the results showed that the visible light absorption intensity was increased significantly due to the reduced band gap and the cavitation effects. As compared to other 3d transition metals, Cu was found to be the most effective one in improving anatase photocatalytic effects. In addition, greater Cu concentration doped in the anatase increased the photocatalysis effects but reduced the anatase stability, therefore, an optimized Cu concentration should be considered to optimize the anatase photocatalysis activity.

Trace doping realizing superior electrochemical performance in P2-type Na_(0.50)Li_(0.08)Mn_(0.60)Co_(0.16)Ni_(0.16)0_(2)cathode for sodium-ion batteries

P2-type layered oxides are receiving significant interest due to their superior structure and intrinsic performances.There are strenuous attempts to balance the structure stability,phase transition as well as desirable electrochemical performances by inducing anion/cation ions,changing morphology,adjusting valence,etc.In this work,several same-period elements of Sc,Ti,V,Cr,Fe,Cu and Zn are doped into Na_(0.50)Li_(0.08)Mn_(0.60)Co_(0.16)Ni_(0.16)O_(2)cathodes,which are manipulated by ions radii and valence state,further studied by operando X-ray powder diffraction patterns(XRD).As a result,the Cu^(2+)doped cathode performed higher rate capacities(as high as 86 mAh/g even at 10 C)and more stable structures(capacity retention of~89.4%for 100 cycles),which owing to the synergistic effect among the tightened TMO_(2)layer,enlarged d-spacing,reduce O-O electrostatic repulsion,ameliorate lattice distortion as well as mitigate ordering of Na^(+)/vacancy.

Reducing the vacancies associated with ferroelectric polarization to promote photocatalytic overall water splitting

Ferroelectric materials hold great promise in photocatalytic water splitting because their built-in electric field induced by the depolarization field can fulfill the separation of photogenerated carriers.However,a number of intrinsic charged vacancy defects are simultaneously generated to screen the depolarized field for stabilizing the crystal structure,always resulting in severe recombination of photogenerated carriers and thus poor overall water splitting activity.Herein,we proposed a strategy to promote the separation and transport of photogenerated carriers of ferroelectric photocatalysts by adjusting the ferroelectric polarization and altering the coordination environment of elements to reduce the defect concentration.Specifically,we prepared a series of Ta-doped PbTiO_(3)with low Pb(V_(Pb))and O(V_(O))vacancy concentrations by reducing the polarization intensity and strengthening the Pb–O interaction.The Ta-doped PbTiO_(3)shows efficient charge separation and greatly enhanced photocatalytic overall water splitting activity with the assistance of cocatalyst.This work highlights the importance of regulating ferroelectric polarization and vacancy defect concentration by the doping strategy in charge separation for photocatalytic water splitting.

Robust tantalum tuned perovskite oxygen electrode for reversible protonic ceramic electrochemical cells

Perovskite oxides with diverse composition and structure have exhibited grand advances in boosting the oxygen reduction and evolution reaction(ORR/OER),which are essential for the reversible protonic ceramic electrochemical cell(R-PCEC)toward the sustainable hydrogen production and utilization.However,enhancement of their activity and stability remains challenging.Herein,we develop the Ta-regulated BaCo_(0.7)Fe_(0.3)O_(3-δ)perovskite oxygen electrode(Ba(Co_(0.7)Fe_(0.3))_(1-x)Ta_xO_(3-δ))with abundant oxygen defects and achieve the simultaneous enhancement in the electrocatalytic activity and stability toward ORR and OER.As-fabricated R-PCEC with(Ba(Co_(0.7)Fe_(0.3))_(0.9)Ta_(0.1)O_(3-δ))(BCFT10)oxygen electrode performs high power density of 1.47 W·cm^(-2)at 650℃in fuel cell mode,and the current density is up to-2.11 A·cm^(-2)at 1.4 V at 650℃in electrolysis mode,as well as the good stability in both the fuel cell and electrolysis modes.Importantly,the cell also demonstrates a stable cycling operation between fuel cell and electrolysis mode,suggesting a great potential of BCFT10 as oxygen electrode material for R-PCECs.

Damage mechanisms and recent research advances in Ni-rich layered cathode materials for lithium-ion batteries

Nickel-rich cathode is considered to be the cathode material that can solve the short-range problem of electric vehicles with excellent elec-trochemical properties and low price.However,microcracks,lithium–nickel hybridization,and irreversible phase transitions during cycling limit their commercial applications.These issues should be resolved by modifications.In recent years,it has been favored by researchers to solve a large number of problems by combining multiple modification strate-gies.Therefore,this paper reviews recent developments in various modification techniques for nickel-rich cathode materials that have improved their electrochemical characteristics.The summary of multiple modifications of nickel-rich materials will play a guiding role in future development.

Structural transformation and magnetic properties of Sm-Fe alloys with V doping

A systematical investigation was carried out on structure and magnetic properties in SmFe_(9-x)V_(x)(x=0.4,0.8,1.2)compounds prepared by a single-roller quenching method.The high cool-down rate leads to metastable TbCu_(7) phase in the parent compound,which gradually transforms into equilibrium ThMn_(12) structure with V-doping content increasing.The Curie temperature increases from 470 to 590 K with V doping,which is consistent with the phase transformation.Surprisingly,simultaneous increase in both coercivity and remanence is resulted by V doping,reaching the highest value of 685 kA·m^(-1)and 44.8×10^(-3)A·m^(2)·g^(-1)in x=1.2 compound,respectively.This phenomenon can be explained by the combination of phase transformation and intergranular exchange coupling throughδM-H plots.

元素掺杂对钠离子电池锰基层状氧化物相变的影响

由于对可再生能源和清洁能源需求的空前增长,以及锂资源的短缺和分布不均,钠离子电池作为有竞争力的替代品越来越受到关注.钠离子层状氧化物材料,特别是锰层状氧化物材料,如P2-Na_(x)MnO_(2),P′2-Na_(x)MnO_(2),P2-Na_(0.67)Ni_(0.33)Mn_(0.67O2),O3-NaNi_(0.5)Mn_(0.5O2)等,具有结构简单、易于合成的优点,因此表现出较高的商业化生产可行性.然而,这些材料普遍面临的挑战是不可逆相变引起的不良循环性能.元素掺杂是抑制不可逆相变,改善材料性能的有效策略.本文综述了锰基层状氧化物材料中元素掺杂的研究进展,并探讨了元素掺杂对晶体结构和结构演化的影响.

Challenges and strategies of lithium-rich layered oxides for Li-ion batteries

Lithium-ion batteries are considered a promising energy storage technology in portable electronics and electric vehicles due to their high energy density,competitive cost,and environmental friendliness.Improving cathode materials is an effective way to meet the demand for better batteries,of which the utilization of high-voltage cathode materials is an important development trend.In recent years,lithium-rich layered oxides have gained great attention due to their desirable energy density.This review presents the relationships between lattice structure and electrochemical properties,the underlying degradation mechanisms,and corresponding modification strategies.The recent progress and strategies are then highlighted,including element doping,surface coating,morphology design,size control,etc.Finally,a concise perspective for future developments and practical applications of lithium-rich layered oxides has been provided.

Introducing Ce ions and oxygen defects into V_(2)O_(5)nanoribbons for efficient aqueous zinc ion storage

Cost-effectively,eco-friendly rechargeable aqueous zinc-ion batteries(AZIBs)have reserved widespread concerns and become outstanding candidate in energy storage systems.However,the progress pace of AZIBs suffers from limitation of suitable and affordable cathode materials.Herein,a double-effect strategy is realized in a one-step hydrothermal treatment to prepare V_(2)O_(5)nanoribbons with intercalation of Ce and introduction of abundant oxygen defects(Od-Ce@V_(2)O_(5))to enhance electrochemical performance synergistically.Coupled with the theoretical calculation results,the introduction of Ce ions intercalation and oxygen vacancies in V2O5 structure enhances the electrical conductivity,reduces the adsorption energy of zinc ions,enlarges the interlayer distance,renders the structure more stable,and facilitates rapid diffusion kinetics.As expected,the desirable cathode delivers the reversible capacity of 444 mAh·g^(−1)at 0.5 A·g^(−1)and shows excellent Coulombic efficiency,as well as an extraordinary energy density of 304.9 Wh·kg^(−1).The strategy proposed here may aid in the further development of cathode materials with stable performance for AZIBs.