Synergistic Effect of Dual-Doped Carbon on MO_(2)C Nanocrystals Facilitates Alkaline Hydrogen Evolution

Molybdenum carbide(MO_(2)C)materials are promising electrocatalysts with potential applications in hydrogen evolution reaction(HER)due to low cost and Pt-like electronic structures.Nevertheless,their HER activity is usually hindered by the strong hydrogen binding energy.Moreover,the lack of water-cleaving site's makes it difficult for the catalysts to work in alkaline solutions.Here,we designed and synthesized a B and N dual-doped carbon layer that encapsulated on MO_(2)C nanocrystals(MO_(2)C@BNC)for accelerating HER under alkaline condition.The electronic interactions between the MO_(2)C nanocrystals and the multiple-doped carbon layer endow a near-zero H adsorption Gibbs free energy on the defective C atoms over the carbon shell.Meanwhile,the introduced B atoms afford optimal H_2O adsorption sites for the water-cleaving step.Accordingly,the dual-doped MO_(2)C catalyst with synergistic effect of non-metal sites delivers superior HER performances of a low overpotential(99 mV@10 mA cm^(-2))and a small Tafel slope(58.1 mV dec^(-1))in 1 M KOH solution.Furthermore,it presents a remarkable activity that outperforming the commercial 10%Pt/C catalyst at large current density,demonstrating its applicability in industrial water splitting.This study provides a reasonable design strategy towards noble-metal-free HER catalysts with high activity.

Cu_(3)P nanoparticles confined in nitrogen/phosphorus dual-doped porous carbon nanosheets for efficient potassium storage

Immobilizing primary electroactive nanomaterials in porous carbon matrix is an effective approach for boosting the electrochemical performance of potassium-ion batteries (PIBs) because of the synergy among functional components. Herein, an integrated hybrid architecture composed of ultrathin Cu_(3)P nanoparticles (~20 nm) confined in porous carbon nanosheets (Cu_(3)P⊂NPCSs) as a new anode material for PIBs is synthesized through a rational self-designed self-templating strategy. Benefiting from the unique structural advantages including more active heterointerfacial sites, intimate and stable electrical contact, effectively relieved volume change, and rapid K^(+) ion migration, the Cu_(3)P⊂NPCSs indicate excellent potassium-storage performance involving high reversible capacity, exceptional rate capability, and cycling stability. Moreover, the strong adsorption of K^(+) ions and fast potassium-ion reaction kinetics in Cu_(3)P⊂NPCSs is verified by the theoretical calculation investigation. Noted, the intercalation mechanism of Cu_(3)P to store potassium ions is, for the first time, clearly confirmed during the electrochemical process by a series of advanced characterization techniques.

Nitrogen/sulphur dual-doped hierarchical carbonaceous fibers boosting potassium-ion storage

The carbon materials as anode electrodes have been widely studied for potassium ion batteries(PIBs).However,the large size of potassium ions prevents their intercalation/deintercalation,resulting in poor storage behaviors.Herein,a novel design of N/S codoped hierarchical carbonaceous fibers(NSHCF)formed from nanosheets self-assembled by catalyzing Aspergillus niger with Sn is reported.The asprepared NSHCF at 600℃(NSHCF-600)exhibits a high reversible capacity of 345.4 m Ah g^(-1) at 0.1 A g^(-1) after 100 cycles and an excellent rate performance of 124.5 m Ah g^(-1) at 2 A g^(-1).The excellent potassium storage performance can be ascribed to the N/S dual-doping,which enlarges interlayer spacing(0.404 nm)and introduces more defects.The larger interlayer spacing and higher pyridinic N active sites can promote K ions diffusion and storage.In addition,the ex situ transmission electron microscopy reveals the high reversibility of potassiation/depotassiation process and structural stability.

Synthesis of dual-doped non-precious metal electrocatalysts and their electrocatalytic activity for oxygen reduction reaction

The pyrolyzed carbon supported ferrum polypyrrole （Fe-N/C） catalysts are synthesized with or without selected dopants, p-toluenesulfonic acid （TsOH）, by a facile thermal annealing approach at desired temperature for optimizing their activity for the oxygen reduction reaction （ORR） in O2-saturated 0.1 mol/L KOH solution. The electrochemical techniques such as cyclic voltammetry （CV） and rotating disk electrode （RDE） are employed with the Koutecky-Levich theory to quantitatively obtain the ORR kinetic constants and the reaction mechanisms. It is found that catalysts doped with TsOH show significantly improved ORR activity relative to the TsOH-free one. The average electron transfer numbers for the catalyzed ORR are determined to be 3.899 and 3.098, respectively, for the catalysts with and without TsOH-doping. The heat-treatment is found to be a necessary step for catalyst activity improvement, and the catalyst pyrolyzed at 600℃ gives the best ORR activity. An onset potential and the potential at the current density of -1.5 mA/cm2 for TsOH-doped catalyst after pyrolysis are 30 mV and 170 mV, which are more positive than those without pyrolized. Furthermore, the catalyst doped with TsOH shows higher tolerance to methanol compared with commercial Pt/C catalyst in 0.1 mol/L KOH. To understand this TsOH doping and pyrolyzed effect, X-ray diffraction （XRD）, scanning electron microscope （SEM） and X-ray photoelectron spectroscopy （XPS） are used to characterize these catalysts in terms of their structure and composition. XPS results indicate that the pyrrolic-N groups are the most active sites, a finding that is supported by the correspondence between changes in pyridinic-N content and ORR activity that occur with changing temperature. Sulfur species are also structurally bound to carbon in the forms of C-Sn-C, an additional beneficial factor for the ORR.

Li-N共掺ZnO纳米管的第一性原理研究

采用基于密度泛函理论的计算方法,系列的研究了锯齿型(9,0)ZnO单壁纳米管、Li,N分别掺杂以及Li-2N共掺杂的ZnO纳米管的能带结构、总体态密度、分波态密度。分析发现虽然Li原子单独掺杂不会对纳米管能带结构产生明显影响,但是Li-2N共掺杂比N单独掺杂ZnO纳米管的结构更加稳定,而且Li-2N共掺杂ZnO纳米管是p型简并半导体。

脉冲激光沉积法Li-N双受主共掺p型ZnO薄膜的生长及其特性

采用脉冲激光沉积技术制备了Li-N双受主共掺杂p型ZnO薄膜,其中Li来自Li掺杂ZnO陶瓷靶,N来自N2O生长气氛.室温Hall测试发现Li-N共掺p型ZnO薄膜的最低电阻率为3.99Ω·cm,迁移率为0.17cm2/(V·s),空穴浓度为9.12×1018cm-3.PL谱测试发现了与Li受主和N受主态相关的发光峰,其受主能级分别约为120和222meV.由p-ZnO:(Li,N)薄膜制备的ZnO同质p-n结具有整流特性.

A lightweight nitrogen/oxygen dual-doping carbon nanofiber interlayer with meso-/micropores for high-performance lithium-sulfur batteries

Lithium-sulfur(Li-S) batteries are promising energy-storage devices for future generations of portable electronics and electric vehicles because of the outstanding energy density,low cost,and nontoxic nature of S.In the past decades,various novel electrodes and electrolytes have been studied to improve the performance of Li-S batteries.However,the very limited lifespan and rate performance of Li-S batteries originating from the dissolution and diffusion of long-chain polysulfides in liquid electrolytes,and the intrinsic poor conductivity of S severely hinder their practical application.Herein,an electrospinning method was developed to fabricate a thin conductive interlayer consisting of meso-/microporous N/O dual-doping carbon nanofiber(CNF).The freestanding 3 D interwoven structure with conductive pathways for electrons and ions can enhance the contact between polysulfides and N/O atoms to realize the highly robust trapping of polysulfides via the extremely polar interaction.Consequently,combining the meso-microporous N/O dual-doping CNF interlayer with a monodispersed S nanoparticle cathode results in a superior electrochemical performance of 862.5 mAh/g after 200 cycles at 0.2 C and a cycle decay as low as 0.08% per cycle.An area specific capacity of 5.22 mAh/cm^(2) can be obtained after 100 cycles at 0.1 C with a high S loading of 7.5 mg/cm^(2).

轻盈柔软 暖意无限:LI-NING新雪丽棉风衣

无论是一件英伦风格的风衣,还是一条能为颈上增添风情万种的围巾,冬天都为精彩穿着创造了无限可能。可是当风雪袭来,气温骤减,爱美之心还是得面对这样一个现实:穿得美必须服从穿得暖的前提。

A combination therapy for androgenic alopecia based on quercetin and zinc/copper dual-doped mesoporous silica nanocomposite microneedle patch

A nanocomposite microneedle(ZCQ/MN)patch containing copper/zinc dual-doped mesoporous silica nanoparticles loaded with quercetin(ZCQ)was developed as a combination therapy for androgenic alopecia(AGA).The degradable microneedle gradually dissolves after penetration into the skin and releases the ZCQ nanoparticles.ZCQ nanoparticles release quercetin(Qu),copper(Cu^(2+))and zinc ions(Zn^(2+))subcutaneously to synergistically promote hair follicle regeneration.The mechanism of promoting hair follicle regeneration mainly includes the regulation of the main pathophysiological phenomena of AGA such as inhibition of dihydrotestosterone,inhibition of inflammation,promotion of angiogenesis and activation of hair follicle stem cells by the combination of Cu^(2+)and Zn^(2+)ions and Qu.This study demonstrates that the systematic intervention targeting different pathophysiological links of AGA by the combination of organic drug and bioactive metal ions is an effective treatment strategy for hair loss,which provides a theoretical basis for development of biomaterial based anti-hair loss therapy.

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.

3D nitrogen and boron dual-doped carbon quantum dots/reduced graphene oxide aerogel for advanced aqueous and flexible quasi-solid-state zinc-ion hybrid capacitors

As prospective energy storage devices,zinc-ion hybrid capacitors(ZHCs)still suffer from unsatisfactory cathode materials.Herein,the three dimensional(3D)N,B dual-doped carbon quantum dots/reduced graphene oxide(N,B-CQDs/rGO)composite aerogel is prepared via a onepot hydrothermal method.Thanks to the synergism of CQDs modification and N,B dual-doping,the resultant N,B-CQDs/rGO composite aerogel delivers superior electrochemical properties.Furthermore,the as-obtained N,B-CQDs/rGO composite aerogel is served as a cathode for aqueous and flexible quasi-solid-state ZHCs for the first time.Impressively,the aqueous N,B-CQDs/rGO//Zn ZHC manifests a large energy density of 96.2 Wh·kg^(-1)at80 W·kg^(-1)and still remains a high energy density of 54.7Wh·kg^(-1)at a superb power density of 80 kW·kg^(-1).Meanwhile,kinetic analyses are employed to elucidate the prominent power performance,and various ex situ tests are undertaken to explore the energy storage mechanism of aqueous ZHC.More notably,the flexible quasi-solid-state N,B-CQDs/rGO//Zn ZHC displays a desirable energy density(89.1μWh·cm^(-2)),a superior power density(96,000μW·cm^(-2))and exceptional flexible performance.The present study offers a valuable reference for designing and developing advanced cathode materials for aqueous and flexible quasi-solid-state ZHCs.

Facile synthesis of Co and Ce dual-doped Ni3S2 nanosheets on Ni foam for enhanced oxygen evolution reaction

Nano Research volume 13,pages2130–2135(2020)Cite this article 376 Accesses 2 Citations Metrics details Abstract Developing efficient and stable oxygen evolution reaction(OER)electrocatalysts via doping strategy has well-documented for electrochemical water splitting.Herein,a homogeneous structure(denoted as Co/Ce-Ni3S2/NF)composed of Co and Ce dual doped Ni3S2 nanosheets on nickel foam was synthesized by a facile one-step hydrothermal method.Co and Ce dopants are distributed inside the host sulfide,thereby raising the active sites and the electrical conductivity.Besides,the CeOx nanoparticles generated by part of the Ce dopants as a cocatalyst further improve the catalytic activity by adding defective sites and enhancing the electron transfer.As a consequence,the obtained Co/Ce-Ni3S2/NF electrode exhibits better electrocatalytic activity than single Co or Ce doped Ni3S2 and pure Ni3S2,with low overpotential(286 mV)at 20 mA-cm^−2,a small Tafel slope and excellent long-term durability in strong alkaline solution.These results presented here not only offer a novel platform for designing transition metal and lanthanide dual-doped catalysts,but also supply some guidelines for constructing catalysts in other catalytic applications.

Covalent Triazine Frameworks-derived N,P Dual-doped Porous Carbons for Highly Efficient Electrochemical Reduction of CO_(2)

Electroreduction of CO_(2)into chemicals is of great importance in the global carbon balance.Although noble-metal based catalysts and single-atom catalysts(SACs)are known to be active for CO_(2)electroreduction reaction(CO_(2)RR),the high cost of noble-metal and the lack of effective synthesis approaches to prepare SACs have tremendously hindered the application.Non-metal doped carbon materials have attracted great interest because of their reasonable cost,chemical stability and excellent electrical conductivity.Nevertheless,the design and fabrication of highly efficient non-metal doped carbon electrocatalysts for CO_(2)RR to meet industry demands still remains a big challenge.Herein,triphenylphosphine@covalent triazine frameworks(CTFs)composites were employed as precursors to fabricate N,P dual-doped porous carbon catalysts PCTF-X-Y(X represents the carbonization temperature,and Y represents the mass ratio of CTF to triphenylphosphine)for CO_(2)RR.Due to the high specific surface areas and synergistic effect between N and P,the obtained PCTF-1000-5 exhibited high selectivity for CO production up to 84.3%at–0.7 V versus the reversible hydrogen electrode(vs.RHE)and long-term durability over 16 h,which are better than the reported N,P dual-doped carbon catalysts in aqueous media.This work provides a new way to design and fabricate non-metal catalysts for electrocatalysis.

Direct insight into sulfiphilicity-lithiophilicity design of bifunctional heteroatom-doped graphene mediator toward durable Li-S batteries

The practical applications of lithium-sulfur(Li-S)battery have been greatly hindered by the severe polysulfide shuttle at the cathode and rampant lithium dendrite growth at the anode.One of the effective solutions deals with concurrent management of both electrodes.Nevertheless,this direction remains in a nascent stage due to a lack of material selection and mechanism exploration.Herein,we devise a temperature-mediated direct chemical vapor deposition strategy to realize the controllable synthesis of three-dimensional boron/nitrogen dual-doped graphene(BNG)particulated architectures,which is employed as a light-weighted and multi-functional mediator for both electrodes in Li-S batteries.Benefiting from the“sulfiphilic”and“lithiophilic”features,the BNG modified separator not only enables boosted kinetics of polysulfide transformation to mitigate the shuttle effect but also endows uniform lithium deposition to suppress the dendritic growth.Theoretical calculations in combination with electro-kinetic tests and operando Raman analysis further elucidate the favorable sulfur and lithium electrochemistry of BNG at a molecular level.This work offers direct insight into the mediator design via controllable synthesis of graphene materials to tackle the fundamental challenges of Li-S batteries.

Boron and nitrogen dual-doped carbon as a novel cathode for high performance hybrid ion capacitors

Hybrid ion capacitors have been considered as a very attractive energy source with high energy density and power density since it combines both merits of lithium ion batteries and supercapacitors. However,their commercial application has been limited by the mismatch of charge-storage capacity and electrode kinetics between the capacitor-type cathode and battery-type anode. Herein, B and N dual-doped 3D superstructure carbon cathode is prepared through a facile template method. It delivers a high specific capacity, excellent rate capability and good cycling stability due to the B, N dual-doping, which has a profound effect in control the porosity, functional groups, and electronic conductivity for the carbon cathode. The hybrid ion capacitors using B, N dual-doping carbon cathode and prelithiated graphite anode show a high energy density of 115.5 Wh/kg at 250 W/kg and remain about 53.6 Wh/kg even at a high power density of 10 kW/kg. Additionally, the novel hybrid device achieves 76.3% capacity retention after 2000 cycles tested at 1250 W/kg power density. Significantly, the simultaneous manipulation of heteroatoms in carbon materials provides new opportunities to boost the energy and power density for hybrid ion capacitors.

Pulse-potential electrochemistry to boost real-life application of pseudocapacitive dual-doped polypyrrole

Polypyrrole(PPy)is a very promising pseudocapacitive electrode material for supercapacitors.However,the poor electrochemical performances and cycling stability caused by volumetric change and counterion drain severely limited its practical application and commercialization.Herein,we present a pulsepotential polymerization strategy for uniformly depositing a dual-doped PPy with ordered and shorter molecular structure by balancing the concentration polarization.Such a strategy ensures more homogeneous stress distribution of PPy during ultralong cycling tests and improves the cycle stability.Moreover,the pulse-potential polymerized PPy with dual anion doping behavior induces enhanced protonation level and improved electrical conductivity,which boosting the charge transfer kinetics.Therefore,the as-synthesized PPy exhibits a remarkable capacitance performance(7250 mF/cm^(2)@3 mA/cm^(2)),outstanding rate capability(3073 mF/cm^(2)@200 mA/cm^(2))and a long cycle life.The assembled symmetric and asymmetric supercapacitors(ASC)exhibit good energy densities(0.8 mWh/cm^(2) for ASC and 0.5 mWh/cm^(2) for symmetric supercapacitor),and excellent durability with zero capacitive loss after 35,000 cycles.In addition,we have fabricated small pouch devices,which can effectively operate a variety of electronic products(including the high-voltage 5 V smartphone,and tablet)and well withstand the external extreme tests during operation,demonstrating the quantitative investigation of the real-life application of aqueous supercapacitors.

Effect of doping order on metal-free heteroatoms dual-doped carbon as oxygen reduction electrocatalyst

Metal-free heteroatoms dual-doped carbon has been recognized as one of the most promising Pt/C-substitutes for oxygen reduction reaction(ORR).Herein,we optimize the preparation process by doping order of metal-free heteroatoms to obtain the best electrocatalytic performance through three types of dual-doped carbon,including XC-N(first X doping then N doping),NC-X(first N doping then X doping) and NXC(N and X doping)(X=P,S and F).XC-N has more defect than the other two indicated by Raman spectra.X-ray photoelectron spectrom(XPS) measurements indicate that N and X have been dual-doped into the carbon matrix with different doping contents and modes,Electrocatalytic results,including the potential of ORR peak(Ep),the half-wave potential,the diffusion-limiting current density mainly follows the order of XC-N>NC-X> NXC,Furthermore,the synergistic effect of second atom doping are also compared with the single doped carbon(NC,PC,SC and FC).The differences in electronegativity and atomic radius of these metal-free heteroatoms can affect the defect degree,the doping content and mode of hete roatoms on carbon matrix,induce polarization effect and space effect to affect O2 adsorption and product desorption,ultimately to the ORR electrocatalytic performance.

Complementary dual-doping of LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)cathode enhances ion-diffusion and stability for Li-ion batteries

The Ni-richLiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)(NCM811)layered cathodes endow Li-ion batteries(LIBs)with high energy density.However,they usually suffer from limited ion-diffusion and structural instability during cycling.Although doping strategy can effectively alleviate these issues,the coupling effects of multi-element doping and the corresponding performance enhancement mechanism have been yet unclear.Here,we report a Zr/Ti dual-doped NCM811 cathode material(ZT-NCM811),in which Zr-ion is doped into both transition metal(TM)layers and lithium layers and Ti-ion is only distributed in TM layers.The dual-doping can effectively enhance crystal structure stability via inhibiting the lattice collapse along c-axis and decreasing the Li/Ni disorder.Meantime,the lattice oxygen escape is also greatly reduced due to the presence of stronger Zr-O and Ti-O bonds,further mitigating the crystal surface parasitic reactions with electrolyte.The resultant ZT-NCM811 exhibits high specific capacity of 124 m Ah/g at even 10 C,much higher than undoped and single-doped NCM811,and a retention of 98.8%at 1 C after 100 cycles.The assembled ZT-NCM811/graphite full cell also delivers superior battery performances and durability.

溶胶-凝胶法制备Li-N双掺p型ZnO薄膜的结构、光学和电学性能

采用溶胶-凝胶法在n型Si(100)衬底上沉积Li-N双掺杂ZnO薄膜,经X射线衍射和扫描电镜图片分析,所制备薄膜具有多晶纤锌矿结构和高的c轴择优取向.室温下霍尔效应测试结果显示Li-N双掺杂ZnO薄膜具有p型导电特性.在Li掺杂量为15.0at%,Li/N(摩尔比)为1∶1,700℃退火等优化条件下得到的最佳电学性能结果是:电阻率为0.34Ω.cm,霍尔迁移率为16.43cm2/V.s,载流子浓度为2.79×1019cm-3.另外,室温下光致发光谱显示,所制备样品具有较强的近紫外和紫光发射,而可见光区范围内与缺陷相关的深能级发射则较微弱.本文还就掺杂浓度和退火温度对薄膜的结构、光学性能以及电学性能的影响进行了讨论.