Pseudocapacitive Heteroatom-Doped Carbon Cathode for Aluminum-Ion Batteries with Ultrahigh Reversible Stability

Aluminum(Al)-ion batteries have emerged as a potential alternative to conventional ion batteries that rely on less abundant and costly materials like lithium.Nonetheless,given the nascent stage of advancement in Al-ion batteries(AIBs),attaining electrode materials that can leverage both intercalation capacity and structural stability remains challenging.Herein,we demonstrate a C3N4-derived layered N,S heteroatom-doped carbon,obtained at different pyrolysis temperatures,as a cathode material for AIBs,encompassing the diffusion-controlled intercalation and surface-induced capacity with ultrahigh reversibility.The developed layered N,S-doped corbon(N,S-C)cathode,synthesized at 900℃,delivers a specific capacity of 330 mAhg^(-1)with a relatively high coulombic efficiency of~85%after 500 cycles under a current density of 0.5 A g^(-1).Owing to its reinforced adsorption capability and enlarged interlayer spacing by doping N and S heteroatoms,the N,S-C900 cathode demonstrates outstanding energy storage capacity with excellent rate performance(61 mAhg^(-1)at 20 A g^(-1))and ultrahigh reversibility(90 mAhg^(-1)at 5Ag^(-1)after 10000cycles).

CoS_(2)nanowires supported graphdiyne for highly efficient hydrogen evolution reaction

Transition metal sulfides are an important category for hydrogen evolution reaction(HER).However,only few edge unsaturated sulfurs functionalize as catalytic sites,which has dramatically limited the catalytic activity and stability.In this work,planar unsaturated sulfurs in(211)plane of the CoS_(2)nanowires have been successfully activated through constructing Graphdiyne-CoS_(2)heterojunction nanocomposites.The corresponding electrons transfer energy barriers for these planar unsaturated sulfurs have been significantly diminished,which are induced by the synergetic effects of the sp~1 hybridized carbons and unsaturated planar sulfurs.In addition,DFT simulations reveal the synergetic effects of the sp~1 hybridized carbons and unsaturated planar sulfurs can promote electron transfer kinetics of the key step,VolmerHeyrovsky step,of the reaction.As expected,the Graphdiyne-CoS_(2)heterojunction nanocomposites exhibit superior HER catalytic performance with low overpotential of 97 mV at 10 mA cm^(-2),and the Tafel slope of 56 mV dec^(-1).Furthermore,the heterojunction shows outstanding stability as well due to the pr tection of the Graphdiyne(GDY).The approach thus paves the way for the further efficient transition metal disulfides catalyst manufactures.

Co-Ru alloy nanoparticles decorated onto two-dimensional nitrogen doped carbon nanosheets towards hydrogen/oxygen evolution reaction and oxygen reduction reaction

Constructing highly-efficient electrocatalysts toward hydrogen evolution reaction(HER)/oxygen evolution reaction(OER)/oxygen reduction reaction(ORR)with excellent stability is quite important for the development of renewable energy-related applications.Herein,Co-Ru based compounds supported on nitrogen doped two-dimensional(2D)carbon nanosheets(NCN)are developed via one step pyrolysis procedure(Co-Ru/NCN)for HER/ORR and following low-temperature oxidation process(Co-Ru@RuO_(x)/NCN)for OER.The specific 2D morphology guarantees abundant active sites exposure.Furthermore,the synergistic effects arising from the interaction between Co and Ru are crucial in enhancing the catalytic performance.Thus,the resulting Co-Ru/NCN shows remarkable electrocatalytic performance for HER(70 mV at 10 mA cm^(-2))in 1 M KOH and ORR(half-wave potential E_(1/2)=0.81 V)in 0.1 M KOH.Especially,the Co-Ru@RuO_(x)/NCN obtained by oxidation exhibits splendid OER performance in both acid(230 mV at 10 mA cm^(-2))and alkaline media(270 mV at 10 mA cm^(-2))coupled with excellent stability.Consequently,the fabricated two-electrode water-splitting device exhibits excellent performance in both acidic and alkaline environments.This research provides a promising avenue for the advancement of multifunctional nanomaterials.

Nickel single atom overcoordinated active sites to accelerate the electrochemical reaction kinetics for Li-S cathode

Lithium-sulfur(Li-S)batteries with high theoretical energy density are promising advanced energy storage devices.However,shuttling of dissolute lithium polysulfide(LiPSs)and sluggish conversion kinetics impede their applications.Herein,single nickel(Ni)atoms on two-dimensional(2D)nitrogen(N)-doped carbon with Ni-N_(4)-O overcoordinated structure(SANi-N_(4)-O/NC)are prepared and firstly used as a sulfur host of Li-S batteries.Due to the efficient polysulfides traps and highly LiPSs conversion effect of SANi-N_(4)-O/NC,the electrochemical performance of Li-S batteries obviously improved.The batteries can well operate even under high sulfur loading(5.8 mg cm^(-2))and lean electrolyte(6.1μL mg^(-1))condition.Meanwhile,density functional theory(DFT)calculations demonstrate that Ni single atom’s active sites decrease the energy barriers of conversion reactions from Li_(2)S_(8)to Li2S due to the strong interaction between SANi-N_(4)-O/NC and LiPSs.Thus,the kinetic conversion of LiPSs was accelerated and the shuttle effect is suppressed on SANi-N_(4)-O/NC host.This study provides a new design strategy for a 2D structure with single-atom overcoordinated active sites to facilitate the fast kinetic conversion of LiPSs for Li-S cathode.

Organophosphine ligand derived sandwich-structural electrocatalyst for oxygen evolution reaction

The synchronous construction of metal phosphate and phosphorus-doped carbon structures is of great significance to innovate the design,synthesis,and application of catalysts,as these phosphoruscontaining composite materials have shown a remarkable contribution to electrocatalysts.However,their preparation procedure generally involves using large amounts of excess phosphorus sources for phosphorization,which inevitably release poisonous PH_(3) or dangerous phosphorus vapor.Here,a strategy for in-situ formation of FePO_(4) embedded in P-doped carbon 2D nano film(FePO_(4)/PdC)is developed using a highly integrated precursor,which is a small molecular organophosphine ligand,1,1’bis(diphenylphosphine)ferrocene(DPPF).The multi-source precursor DPPF that contains Fe,P,and C is molecular-vapor-deposited on the nickel foam(NF)supported ZIF-67 nanosheets to obtain the composite catalyst,namely DPPF-500/ZIF-67/NF.FePO_(4)/PdC encapsulated the ZIF-67 derived Co/N-doped carbon matrix(Co NC)to form a sandwich structure FePO_(4)/PdC@CoNC.The constructed catalyst shows good performance for OER,requiring an overpotential of only 297 m V to deliver 600 m A/cm^(2) with a Tafel slope of 42.7 m V dec^(-1).DFT calculations demonstrate that the synergistic effects between the metal active center and P-doped carbon film reduce the energy barriers and improve electron transport.This method of constructing P-containing catalysts overcomes the demand for additional P sources to realize eco-friendly fabrication and yields a unique structure with good catalytic activity.

2D–3D dual carbon layer confined ultrasmall VN nanoparticles for improving lithium-ion storage in hybrid capacitors

Lithium-ion capacitors(LICs) of achieving high power and energy density have garnered significant attention. However, the kinetics unbalance between anode and cathode can impede the application of LICs. Vanadium nitride(VN) with a high theoretical specific capacity(~ 1200 m Ah·g^(-1)) is a better pseudocapacitive anode to match the response of cathode in LICs. However, the insertion/extraction of Li-ions in VN's operation results in significant volume expansion. Herein, the VN/N-r GO-5composite that three-dimentional(3D) dicyandiamidederived-carbon(DDC) tightly wrapped VN quantum dots(VN QDTs) on two-dimentional(2D) reduced graphene oxid(r GO) was prepared by a facile strategy. The VN QDTs can reduce ion diffusion length and improve charge transfer kinetics. The 2D r GO as a template provides support for nanoparticle dispersion and improves electrical conductivity. The 3D DDC tightly encapsulated with VN QDTs mitigates agglomeration of VN particles as well as volume expansion. Correspondingly, the LICs with VN/Nr GO-5 composite as anode and activated carbon(AC) as cathode were fabricated, which exhibits a high energy density and power density. Such strategy provides a perspective for improving the electrochemical properties of LIC anode materials by suppressing volume expansion and enhancing conductivity.

Tunable 2D tremella-derived carbon nanosheets with enhanced pseudocapacitance behavior for ultrafast potassium-ion storage

The sluggish intercalation kinetics of potassium ions in various anode materials severely hinders the practical application of potassium ion batteries(PIBs) in the field of new energy storage. To overcome this difficulty, we developed a green and recyclable molten-salt(MS) strategy using natural tremella as raw material to construct self-N-doped two-dimensional(2D)tremella-derived carbon nanosheets(TCNs), which possesses large specific surface area(SSA), expanded interlayer spacing and rich defects/active sites. Thanks to the unique 2D nanosheet structure and self-N doping, TCNs800 electrode exhibits superior K+storage capacity(386.3 mA h g^(-1) at 0.1 A g^(-1)), ultrafast rate performance(119.7 mA h g^(-1) at 2.0 A g^(-1)) and long-term cycling stability(122.9 mA h g^(-1) with the Coulombic efficiency of near 100% after 1000 cycles). Moreover, detailed electrochemical kinetic analysis shows that the potassium-ion storage mechanism of TCNs800 electrode has enhanced by the pseudocapacitancecontrolled behavior. This work proves an effective green and environmentally friendly MS strategy to prepare 2D biomass nanosheet materials, and provides a reference for exploring excellent electrode materials with pseudocapacitance-controlled behavior.

Enhanced visible-light photocatalytic hydrogen evolution using two-dimensional carbon nitride sheets with the removal of amine groups

Two-dimensional(2D)carbon nitride sheets(CNs)with atomically thin structures are regarded as one of the most promising materials for solar energy conversion.However,due to their substantially enlarged bandgap caused by the strong quantum size effect and their incomplete polymerisation with a large number of non-condensed surface amino groups,the practical applicability of CNs in photocatalysis is limited.In this study,CNs with broad visible-light absorption were synthesised using a 5-min fast thermal annealing.The removal of uncondensed amine groups reduces the bandgap of CNs from 3.06 eV to 2.60 eV,increasing their absorption of visible light.Interestingly,the CNs were distorted after annealing,which can differentiate the spatial positions of electrons and holes,enhancing the visible-light absorption efficiency.As a result,when exposed to visible light,the photocatalytic hydrogen production activity of atomically thin 2D CNs rose by 8.38 times.This research presents a dependable and speedy method for creating highly effective visible-light photocatalysts with narrowed bandgaps and improved visible-light absorption.

Heterointerface engineering of assembled CoP_(2) on N-modified carbon as efficient trifunctional electrocatalysts for Zn-Air batteries and overall water splitting

Enhancing catalytic activity through modulating the interaction between N-doped carbon and metal phosphides clusters is an effective approach.Herein,the electronic structure modulation of CoP_(2) supported N-modified carbon(CoP_(2)/NC)has been designed and prepared as efficient electrocatalysts for oxygen reduction reaction(ORR),oxygen evolution reaction(OER),and hydrogen evolution reaction(HER).Notably,CoP_(2)/NC-1 catalyst exhibits impressive performance in alkaline media,with an ORR half-wave potential of 0.84 V,as well as OER and HER overpotentials of 290 and 129 mV(at 10 mA·cm^(−2)),respectively.In addition,CoP_(2)/NC-1 produces a power density as high as 172.9 mW·cm^(−2),and excellent reversibility of 100 h at 20 mA·cm^(−2) in home-made Zn-air batteries.The experimental results demonstrate that the synergistic interactions between N modified carbon substrate and CoP_(2) material significantly enhance the kinetics of ORR,OER,and HER.Density functional theory(DFT)calculations reveal the strong electrons redistribution of CoP_(2) induced by high-density N atoms at the interface,thus optimizing the key intermediates and significantly lower the energy barrier of reactions.These electronic adjustments of CoP_(2) greatly enhance its kinetics of ORR/OER/HER,leading to faster reactions.This study provides profound insights into the specific modification of CoP_(2) by N-doped carbon,enabling the construction of efficient catalysts.

UV light driven high-performance room temperature surface acoustic wave NH_(3) gas sensor using sulfur-doped g-C_(3)N_(4) quantum dots

Nanomaterials integrated surface acoustic wave(SAW)gas sensing technology has emerged as a promising candidate for realtime toxic gas sensing applications for environmental and human health safety.However,the development of novel chemical interface based on two-dimensional(2D)sensing materials for SAW sensors for the rapid and sensitive detection of NH_(3)gas at room temperature(RT)still remains challenging.Herein,we report a highly selective RT NH_(3)gas sensor based on sulfur-doped graphitic carbon nitride quantum dots(S@g-C_(3)N_(4)QD)coated langasite(LGS)SAW sensor with enhanced sensitivity and recovery rate under ultraviolet(UV)illumination.Fascinatingly,the sensitivity of the S@g-C_(3)N_(4)QD/LGS SAW sensor to NH_(3)(500 ppb)at RT is dramatically enhanced by~4.5-fold with a low detection limit(~85 ppb),high selectivity,excellent reproducibility,fast response/recovery time(70 s/79 s)under UV activation(365 nm)as compared to dark condition.Additionally,the proposed sensor exhibited augmented NH_(3)detection capability across the broad range of relative humidity(20%–80%).Such remarkable gas sensing performances of the as-prepared sensor to NH_(3)are attributed to the high surface area,enhanced functional groups,sulfur defects,UV photogenerated charge carriers,facile charge transfer in the S@g-C_(3)N_(4)QD sensing layer,which further helps to improve the gas molecules adsorption that causes the increase in conductivity,resulting in larger frequency responses.The gas sensing mechanism of S@g-C_(3)N_(4)QD/LGS SAW sensor is ascribed to the enhanced electroacoustic effect,which is supported by the correlation of resistive type and COMSOL Multiphysics simulation studies.We envisage that the present work paves a promising strategy to develop the next generation 2D g-C_(3)N_(4)based high responsive RT SAW gas sensors.