The development of metal-free carbon catalysts has garnered significant attention as a promising approach to address the challenges of sustainable catalysis,particularly in the replacement of toxic and environmentally...The development of metal-free carbon catalysts has garnered significant attention as a promising approach to address the challenges of sustainable catalysis,particularly in the replacement of toxic and environmentally hazardous mercury-based systems for the coal-based PVC industry.Within a decade of development,the catalytic performance of carbon catalysts has been improved greatly and even shows superiorities over metal catalysts in some cases,which have demonstrated great potential as sustainable alternatives to mercury catalysts.This review provides a comprehensive summary of the recent advancements in carbon catalysts for acetylene hydrochlorination.It encompasses a wide range of aspects,including the identification of active sites from heteroatom doping to intrinsic carbon defects,the various synthetic strategies employed,the reaction and deactivation mechanisms of carbon catalysts,and the current insights into the key challenges that are encountered on the journey from laboratory research to scalable commercialization within the field of carbon catalysts.The review offers foundational insights and practical guidelines for designing green carbon catalysts systems,not only for acetylene hydrochlorination but also for other heterogeneous catalytic reactions.展开更多
While heteroatom doping serves as a powerful strategy for devising novel polycyclic aromatic hydrocarbons(PAHs), the further fine-tuning of optoelectronic properties via the precisely altering of doping patterns remai...While heteroatom doping serves as a powerful strategy for devising novel polycyclic aromatic hydrocarbons(PAHs), the further fine-tuning of optoelectronic properties via the precisely altering of doping patterns remains a challenge. Herein, by changing the doping positions of heteroatoms in a diindenopyrene skeleton, we report two isomeric boron, sulfur-embedded PAHs, named Anti-B_(2)S_(2) and Syn-B_(2)S_(2), as electron transporting semiconductors. Detailed structure-property relationship studies revealed that the varied heteroatom positions not only change their physicochemical properties, but also largely affect their solid-state packing modes and Lewis base-triggered photophysical responses. With their low-lying frontier molecular orbital levels, n-type characteristics with electron mobilities up to 1.5 × 10^(-3)cm^(2)V^(-1)s^(-1)were achieved in solution-processed organic field-effect transistors. Our work revealed the critical role of controlling heteroatom doping patterns for designing advanced PAHs.展开更多
Carbon dioxide(CO_(2))reduction into chemicals or fuels by electrocatalysis can eff ectively reduce greenhouse gas emissions and alleviate the energy crisis.Currently,CO_(2)electrocatalytic reduction(CO_(2)RR)has been...Carbon dioxide(CO_(2))reduction into chemicals or fuels by electrocatalysis can eff ectively reduce greenhouse gas emissions and alleviate the energy crisis.Currently,CO_(2)electrocatalytic reduction(CO_(2)RR)has been considered as an ideal way to achieve“carbon neutrality.”In CO_(2)RR,the characteristics and properties of catalysts directly determine the reaction activity and selectivity of the catalytic process.Much attention has been paid to carbon-based catalysts because of their diversity,low cost,high availability,and high throughput.However,electrically neutral carbon atoms have no catalytic activity.Incorpo-rating heteroatoms has become an eff ective strategy to control the catalytic activity of carbon-based materials.The doped carbon-based catalysts reported at present show excellent catalytic performance and application potential in CO_(2)RR.Based on the type and quantity of heteroatoms doped into carbon-based catalysts,this review summarizes the performances and catalytic mechanisms of carbon-based materials doped with a single atom(including metal and without metal)and multi atoms(including metal and without metal)in CO_(2)RR and reveals prospects for developing CO_(2)electroreduction in the future.展开更多
Replacing fossil fuels with fuel cells is a feasible way to reduce global energy shortages and environmental pollution.However,the oxygen reduction reaction(ORR)at the cathode has sluggish kinetics,which limits the de...Replacing fossil fuels with fuel cells is a feasible way to reduce global energy shortages and environmental pollution.However,the oxygen reduction reaction(ORR)at the cathode has sluggish kinetics,which limits the development of fuel cells.It is significant to develop catalysts with high catalytic activity of ORR.The single-atom catalysts(SACs)of Pt supported on heteroatom-doped graphene are potential candidates for ORR.Here we studied the SACs of Pt with different heteroatoms doping and screened out Pt-C_(4) and Pt-C_(3)O_(1) structures with only 0.13 V overpotential for ORR.Meanwhile,it is found that B atoms doping could weaken the adsorption capacity of Pt,while N or O atoms doping could enhance it.This regularity was verified on Fe SACs.Through the electronic interaction analysis between Pt and adsorbate,we explained the mechanism of this regularity and further proposed a new descriptor named corrected d-band center(ε_(d-corr))to describe it.This descriptor is an appropriate reflection of the number of free electrons of the SACs,which could evaluate its adsorption capacity.Our work provides a purposeful regulatory strategy for the design of ORR catalysts.展开更多
Activated carbon(AC)has attracted tremendous research interest as an electrode material for supercapacitors owing to its high specific surface area,high porosity,and low cost.However,AC-based supercapacitors suffer fr...Activated carbon(AC)has attracted tremendous research interest as an electrode material for supercapacitors owing to its high specific surface area,high porosity,and low cost.However,AC-based supercapacitors suffer from limited rate performance and low power density,which mainly arise from their inherently low electrical conductivity and sluggish ion dynamics in the micropores.Here,we propose a simple yet effective strategy to address the aforementioned issue by nitrogen/fluorine doping and enlarging the micropore size.During the treatment,the decomposition products of NH4F react with the carbon atoms to dope the AC with nitrogen/fluorine and simultaneously enlarge the pores by etching.The treated AC shows a higher specific surface area of 1826 m2 g^(−1)(by~15%),more micropores with a diameter around 0.93 nm(by~33%),better wettability(contact angle decreased from 120°to 45°),and excellent electrical conductivity(96 S m^(−1))compared with untreated AC(39 S m^(−1)).The as-fabricated supercapacitors demonstrate excellent specific capacitance(26 F g^(−1)at 1 A g^(−1)),significantly reduced electrical resistance(by~50%),and improved rate performance(from 46.21 to 64.39%at current densities of 1 to 20 A g^(−1)).Moreover,the treated AC-based supercapacitor achieves a maximum energy density of 25 Wh kg^(−1)at 1000 W kg^(−1)and a maximum power density of 10,875 W kg^(−1)at 15 Wh kg^(−1),which clearly outperforms pristine AC-based supercapacitors.This synergistic treatment strategy provides an effective way to improve the rate performance and power density of AC-based supercapacitors.展开更多
Zinc-ion hybrid supercapacitors(ZHSs)are highly desirable for large-scale energy storage applications owing to the merits of high safety,low cost and ultra-long cycle life.The poor rate performance of cathodes,however...Zinc-ion hybrid supercapacitors(ZHSs)are highly desirable for large-scale energy storage applications owing to the merits of high safety,low cost and ultra-long cycle life.The poor rate performance of cathodes,however,severely hinders their application.Herein,aqueous ZHSs with superior performance were fabricated by employing a series of ultrathin carbon nanobelts modified with B,N,O(CPTHBBx).The heteroatom doping can significantly modify the chemical behaviors of carbon frameworks,which could generate numerous active sites and accelerate the charge transport.The systematic investigation reveals that the B-N groups are active species for fast Zn-ion adsorption and desorption.As a result,the best-performed CPTHB-B2 exhibits an excellent electrochemical performance as cathodes in ZHSs,delivering a high specific capacitance of 415.3 F g^(−1) at 0.5 A g^(−1),a record high capacitance retention of 81%when increasing the current densities from 0.5 to 100 A g^(−1),an outstanding energy density of 131.9 W h kg^(−1) and an exceptionally high power density of 42.1 kW kg^(−1).Our work provides a new cathode design for ultrafast charging Zn-ion storage devices.展开更多
The development of single atom catalysts(SACs)with asymmetric active sites by defect regulation provides an encourage potential for oxygen reduction reaction(ORR)and hydrogen evolution reaction(HER),but highly challen...The development of single atom catalysts(SACs)with asymmetric active sites by defect regulation provides an encourage potential for oxygen reduction reaction(ORR)and hydrogen evolution reaction(HER),but highly challenging.Herein,N-doped carbon(N-C)anchored atomically dispersed Ni-N_(3)site with proximity defects(Ni-N_(3)D)induced by Te atoms doping is reported.Benefitting from the inductive effect of proximity defect,the Ni-N_(3)D/Te-N-C catalyst performs excellent ORR and HER performance in alkaline and acid condition.Both in situ characterization and theoretical calculation reveal that the existence of proximity defect effect is conducive to lower rate-determining-step energy barrier of ORR and HER,thus accelerating the multielectron reaction kinetics.This work paves a novel strategy for constructing highactivity bifunctional SACs by defect engineering for development of sustainable energy.展开更多
The Ni single-atom catalyst dispersed on nitrogen doped graphene support has attracted much interest due to the high selectivity in electro-catalyzing CO_(2)reduction to CO,yet the chemical inertness of the metal cent...The Ni single-atom catalyst dispersed on nitrogen doped graphene support has attracted much interest due to the high selectivity in electro-catalyzing CO_(2)reduction to CO,yet the chemical inertness of the metal center renders it to exhibit electrochemical activity only under high overpotentials.Herein,we report P-and S-doped Ni single-atom catalysts,i.e.symmetric Ni_(1)/PN_(4)and asymmetric Ni1/SN_(3)C can exhibit high catalytic activity of CO_(2)reduction with stable potential windows.It is revealed that the key intermediate*COOH in CO_(2)electroreduction is stabilized by heteroatom doping,which stems from the upward shift of the axial d_(z2)orbital of the active metal Ni atom.Furthermore,we investigate the potential-dependent free energetics and dynamic properties at the electrochemical interface on the Ni1/SN3C catalyst using ab initio molecular dynamics simulations with a full explicit solvent model.Based on the potential-dependent microkinetic model,we predict that S-atom doped Ni SAC shifts the onset potential of CO_(2)electroreduction from–0.88 to–0.80 V vs.RHE,exhibiting better activity.Overall,this work provides an in-depth understanding of structure-activity relationships and atomic-level electrochemical interfaces of catalytic systems,and offers insights into the rational design of heteroatom-doped catalysts for targeted catalysis.展开更多
Electrochemical CO_(2) reduction reaction(CO_(2)RR) into valuable formate provides a strategy for carbon neutrality.Bismuth(Bi) catalysts,attributed to their appropriate energy barrier of OCHO*intermediate,have demons...Electrochemical CO_(2) reduction reaction(CO_(2)RR) into valuable formate provides a strategy for carbon neutrality.Bismuth(Bi) catalysts,attributed to their appropriate energy barrier of OCHO*intermediate,have demonstrated substantial potential for the advancement of electrocatalytic CO_(2) reduction to formate.However,due to the weak bonding of protons(H^(*)) of Bi,the available protonate of CO_(2) on Bi is insufficient,which limits the formation of OCHO^(*).Prediction by theoretical calculation,chlorine doping can effectively promote the dissociation of H_(2)O and thus achieve effective proton supply.We prepare chlorine-doped Bi(Cl-Bi) via an electrochemical conversion strategy for electroreduction of CO_(2) .An obvious improvement of faradaic efficiency(FE) of formate(96.7% at-0.95 V vs.RHE) can be achieved on Cl-Bi,higher than that of Bi(89.4%).Meanwhile,Cl-Bi has the highest formate production rate of 275 μmol h^(-1)cm^(-2)at-0.95 V vs.RHE,which is 1.2 times higher than that of Bi(224 μmol h^(-1)cm^(-2)).In situ characterizations and kinetic analysis reveal that chlorine doping promotes the activation of H_(2)O and supply sufficient protons to promote the protonation of CO_(2) to OCHO^(*),which is consistent with theoretical calculation.The study presents an effective strategy for rational design of highly efficient electrocatalysts to promote green chemical production.展开更多
Lithium-sulfur batteries(LSBs)have received much concern as emerging high-power energy storage system.Nevertheless,the low conductivity of sulfur and poly sulfide shuttle results in low rate capability and rapid capac...Lithium-sulfur batteries(LSBs)have received much concern as emerging high-power energy storage system.Nevertheless,the low conductivity of sulfur and poly sulfide shuttle results in low rate capability and rapid capacity decay,which seriously limit its commercial application.Here,facile,sustainable and cost-effective strategy for preparing heteroatom-doped porous activated carbon(PAC)derived from biomass palm kernel shell(PKS)was developed for high-performance LSB applications.The presence of N,P and S heteroatoms with modification of the surface polarity brings about large amounts of active sites and improved adsorption property compared to those of common carbon materials.The PAC sample possesses desirable specific surface area(SSA)(2760 m2·g-1)as well as pore volume(1.6 cm3·g-1).Besides,the good electrical conductivity of PAC endows the material with excellent rate performance.The PAC-S electrode with a 60%of sulfur loading has a desirable first discharge capacity(1045 mAh·g1,200 mA·g-1)with superb discharge capacity(869.8 mAh·g-1,100 th cycle)and cyclability(312.6 mAh·g-1,800 mA·g-1,1000 th cycle),which can be mainly ascribed to its unique porous properties and the good conductivity of PAC.展开更多
Developing high-efficiency multifunctional nanomaterials is promising for wide p H hydrogen evolution reaction(HER) and energy storage but still challenging. Herein, a novel in-situ doping-induced lattice strain strat...Developing high-efficiency multifunctional nanomaterials is promising for wide p H hydrogen evolution reaction(HER) and energy storage but still challenging. Herein, a novel in-situ doping-induced lattice strain strategy of NiCoP/S nanocrystals(NCs) was proposed through using seed crystal conversion approach with NiCo_(2)S_(4) spinel as precursor. The small amount of S atoms in NiCoP/S NCs perturbed the local electronic structure, leading to the atomic position shift of the nearest neighbor in the protocell and the nanoscale lattice strain, which optimized the H* adsorption free energy and activated H_(2)O molecules, resulting the dramatically elevated HER performance within a wide p H range. Especially, the NiCoP/S NCs displayed better HER electrocatalytic activity than comical 20% Pt/C at high current density in 1 M KOH and natural seawater: it only needed 266 m V vs. reversible hydrogen electrode(RHE) and660 m V vs. RHE to arrive the current density of 350 m A cm^(-2) in 1 M KOH and natural seawater, indicating the application prospect for industrial high current. Besides, NiCoP/S NCs also displayed excellent supercapacitor performance: it showed high specific capacity of 2229.9 F g^(-1) at 1 A g^(-1) and energy density of87.49 Wh kg^(-1), when assembled into an all-solid-state flexible device, exceeding performance of most transition metal phosphides. This work provides new insights into the regulation in electronic structure and lattice strain for electrocatalytic and energy storage applications.展开更多
Zinc ion capacitors(ZICs)have drawn increas-ing interest in energy storage devices because of their economic benefits,high safety,and long cycling life.Nevertheless,the lack of high-performance cathodes for ZICs remai...Zinc ion capacitors(ZICs)have drawn increas-ing interest in energy storage devices because of their economic benefits,high safety,and long cycling life.Nevertheless,the lack of high-performance cathodes for ZICs remains a key challenge.Here,we fabricated B,N co-doped porous carbon(BN-C)via a salt template strategy.The aqueous ZICs assembled from BN-C cathode delivered a high capacity of 190.2 mAh·g^(-1)and a remarkable energy density of 105.1 Wh·kg^(-1).Moreover,systematic charac-terization verifies that B/N dual-doping promotes the physical adsorption/desorption kinetics of anion and the chemical absorption/desorption kinetics of Zn^(2+),thus improving the electrochemical performance of ZICs.In addition,the quasi-solid-state pouch-type battery exhibited excellent electrochemical durability and mechanical flexi-bility,demonstrating its vast application potential as a flexible power source.Overall,this research not only pre-sents a reasonable approach to the large-scale production of carbon cathode materials with excellent electrochemical performance but also strengthens the essential recognition of the charge storage mechanism of heteroatoms-doped carbon materials.展开更多
Hydrazine-assisted water electrolysis is a promising energy conversion technology for highly efficient hydrogen production.Rational design of bifunctional electrocatalysts,which can simultaneously accelerate hydrogen ...Hydrazine-assisted water electrolysis is a promising energy conversion technology for highly efficient hydrogen production.Rational design of bifunctional electrocatalysts,which can simultaneously accelerate hydrogen evolution reaction(HER)/hydrazine oxidation reaction(HzOR)kinetics,is the key step.Herein,we demonstrate the development of ultrathin P/Fe co-doped NiSe_(2) nanosheets supported on modified Ni foam(P/Fe-NiSe_(2)) synthesized through a facile electrodeposition process and subsequent heat treatment.Based on electrochemical measurements,characterizations,and density functional theory calculations,a favorable“2+2”reaction mechanism with a two-step HER process and a two-step HzOR step was fully proved and the specific effect of P doping on HzOR kinetics was investigated.P/Fe-NiSe_(2) thus yields an impressive electrocatalytic performance,delivering a high current density of 100 mA cm^(−2) with potentials of−168 and 200 mV for HER and HzOR,respectively.Additionally,P/Fe-NiSe_(2) can work efficiently for hydrazine-assisted water electrolysis and Zn-Hydrazine(Zn-Hz)battery,making it promising for practical application.展开更多
Constructing anodes with fast ions/electrons transfer paths is an effective strategy to achieve high-performance sodium ion batteries(SIBs)/potassium ion batteries(PIBs). Amorphous carbon is a promising candidate anod...Constructing anodes with fast ions/electrons transfer paths is an effective strategy to achieve high-performance sodium ion batteries(SIBs)/potassium ion batteries(PIBs). Amorphous carbon is a promising candidate anode for SIBs/PIBs owing to its disordered carbon layers, abundant defects/pores, and lowcost resources. However, the larger radius of Na^(+)/K^(+) leading to depressed kinetics and poor cycling performance, impeding their further applications. Herein, we propose an efficient strategy to construct of nitrogen, sulfur co-doped hollow carbon nanospheres(NS-HCS) involving an in situ growth of polydopamine on nano-Ni(OH)2template with subsequent sulfur doping process. During the formation process, the produced Ni nanospheres play as the hard template and catalyst for the formation of hollow carbon nanosphere with partially graphite microcrystalline structure, while the sulfur doping process can enlarge the interlayer space and create more defects on the surface of carbon nanospheres, thus synchronous improve the Na^(+)/K^(+) insertion and adsorption ability in NS-HCS. With the synergistic control of the enlarged interlayer spacing, high content of pyridinic N/pyrrolic N and graphitization, a hybrid storage mechanism facilitates the transport kinetics and endows the NS-HCS electrode with high capacities and good cycling stability in SIBs and PIB. Benefit from the multiple effects, NS-HCS exhibits the improved capacity of 274.8 m Ah/g at 0.1 A/g and excellent cycling stability of 149.5 m Ah/g after 5000 cycles at2.5A/g in SIBs, as well as good potassium ion storage behavior with a high capacity retention of 76.5%after 700 cycles at 1.0 A/g, demonstrating the potential applications of NS-HCS for high-performance SIBs and PIBs.展开更多
Banana peel-derived porous carbon(BPPC) was prepared from banana peel and used as an adsorbent for methyl orange(MO) wastewater removal. BPPC-MO50 is a N,S-doped BPPC obtained via secondary carbonization. The BPPC-MO5...Banana peel-derived porous carbon(BPPC) was prepared from banana peel and used as an adsorbent for methyl orange(MO) wastewater removal. BPPC-MO50 is a N,S-doped BPPC obtained via secondary carbonization. The BPPC-MO50 exhibited a high specific surface area of1774.3 m^2/g. Heteroatom-doped porous carbon(PC) was successfully synthesized from the BPPC absorbed MO at high temperature and used for oxygen reduction. The BPPC-MO50 displayed the highest ORR onset potential among all carbon-based electrocatalysts, i.e., 0.93 V vs.reversible hydrogen electrode(RHE). This is the first report to describe porous carbon-activated materials from agriculture and forestry waste that is used for adsorption of dyes from wastewater via an enhanced heteroatom(N,S) content. These results may contribute to the sustainable development of dye wastewater treatment by transforming saturated PC into an effective material and has potential applications in fuel cells or as energy sources.展开更多
The search for non-precious and efficient electrocatalysts towards the oxygen evolution reaction(OER)is of vital importance for the future advancement of multifarious renewable energy conversion/storage technologies.E...The search for non-precious and efficient electrocatalysts towards the oxygen evolution reaction(OER)is of vital importance for the future advancement of multifarious renewable energy conversion/storage technologies.Electronic modulation via heteroatom doping is recognized as one of the most forceful leverages to enhance the electrocatalytic activity.Herein,we demonstrate a delicate strategy for the in-situ confinement of S-doped Ni O nanoparticles into N-doped carbon nanotube/nanofiber-coupled hierarchical branched superstructures(labeled as S-Ni O@N-C NT/NFs).The developed strategy simultaneously combines enhanced thermodynamics via electronic regulation with accelerated kinetics via nanoarchitectonics.The S-doping into Ni O lattice and the 1 D/1 D-integrated hierarchical branched carbon substrate confer the resultant S-Ni O@N-C NT/NFs with regulated electronic configuration,enriched oxygen vacancies,convenient mass diffusion pathways and superior architectural robustness.Thereby,the SNi O@N-C NT/NFs display outstanding OER properties with an overpotential of 277 m V at 10 m A cm^(-2)and impressive long-term durability in KOH medium.Density functional theory(DFT)calculations further corroborate that introducing S-dopant significantly enhances the interaction with key oxygenate intermediates and narrow the band gap.More encouragingly,a rechargeable Zn-air battery using an air-cathode of Pt/C+S-Ni O@N-C NT/NFs exhibits a lower charge voltage and preferable cycling stability in comparison with the commercial Pt/C+Ru O_(2)counterpart.This study highlighting the concurrent consideration of electronic regulation,architectural design and nanocarbon hybridization may shed light on the future exploration of economical and efficient electrocatalysts.展开更多
Modulate the electronic structure and surface energy by nanostructure and heteroatom doping is an efficient strategy to improve electrocatalytic activity of hydrogen evolution reaction(HER).Herein,nickel incorporated ...Modulate the electronic structure and surface energy by nanostructure and heteroatom doping is an efficient strategy to improve electrocatalytic activity of hydrogen evolution reaction(HER).Herein,nickel incorporated WP_(2) self-supporting nanosheet arrays cathode was synthesized on carbon cloth(Ni-WP_(2) NS/CC)by in-situ phosphating reduction of the Ni-doped WO3.It shows that heteroatom doping and the three-dimensional(3D)nanosheet arrays morphology both facilitate to reduce the interfacial transfer resistance and increase electrochemical-active surface areas,which effectively improve electrocatalytic hydrogen evolution reaction(HER)activity.The optimized catalyst,1%Ni-WP_(2) NS/CC,exhibits an outstanding electrocatalytic performance with an overpotential of 110 m V at 10 m A cm^(-2) and a Tafel slope of 65 m V dec^(-1) in the acid solution.DFT calculations further demonstrate the nickel doping can adjust the intrinsic structure of electronics,lower the Gibbs free energy of adsorption of hydrogen(DGH*),and effectively improve the HER performance.展开更多
Electrocatalysts play a crucial role in the development of renewable energy conversion and storage nanotechnologies.The unique advantages of heteroatom-doped porous carbon-supported single-atom electrocatalysts(SAC-HD...Electrocatalysts play a crucial role in the development of renewable energy conversion and storage nanotechnologies.The unique advantages of heteroatom-doped porous carbon-supported single-atom electrocatalysts(SAC-HDPCs)are clear.These SAC-HDPCs exhibit outstanding activity,selectivity and stability due to their distinct electronic structure,satisfactory conductivity,controllable porosity and heteroatomdoping effect.Rapid and significant developments involving the synthesis,characterization,and structure-property-function relationship of SAC-HDPCs have been made in recent years.In this review,we describe recent research efforts involving advanced(in situ)characterization techniques,innovative synthetic strategies,and electrochemical energy conversion examples of SAC-HDPCs.The electrocatalytic performance of SAC-HDPCs is further considered at an atomic level,and the mechanisms underlying this performance are also discussed in detail.We expect that these analyses and deductions will be useful for the design of new materials and may help to establish a foundation for the design of future SAC-HDPCs.展开更多
CoPS nanoparticles encapsulated with S,P,N tri-doped carbon material(SPNC)were proposed as bifunctional electrocatalyst of oxygen evolution reaction(OER)and oxygen reduction reaction(ORR)derived from zeolitic imidazol...CoPS nanoparticles encapsulated with S,P,N tri-doped carbon material(SPNC)were proposed as bifunctional electrocatalyst of oxygen evolution reaction(OER)and oxygen reduction reaction(ORR)derived from zeolitic imidazolate framework-67.Density functional theory calculations consistently revealed that P element in CoPS@SPNC improves the electrical conductivity and reduces OH^(*)hydrogenation energy barrier on Co sites,thereby facilitating the overall ORR/OER activities.A flexible Zn–air battery with CoPS@SPNC delivered an overpotential of 0.49 V,an energy efficiency above 80%,and a discharge voltage of 1.29 V at 2 mA cm^(-2) for 80 h.展开更多
Heteroatom-doped transition metal oxides have attracted great attention as advanced anode materials for lithium-ion batteries due to their high theoretical capacity and superior properties.However,the limited resource...Heteroatom-doped transition metal oxides have attracted great attention as advanced anode materials for lithium-ion batteries due to their high theoretical capacity and superior properties.However,the limited resource availability has led to a substantial rise in prices for valuable metals such as Ni and Co,posing a significant challenge for their application.To address this issue,recycling of these metals from waste materials have gained prominence,and particularly the recovery of Co has been mostly focused on its economic benefits.Herein,we introduced a novel recycling strategy for fabrication of heteroatomdoped CoO_(x)(comprising mainly Co_(3)O_(4)with a minor CoO phase)anode with a yolk–shell structure for lithium-ion batteries,by separating Co from cemented tungsten carbide waste.By employing a simple leaching process and subsequent spray pyrolysis,the yolk–shell structured microsphere comprising CoO_(x)was successfully synthesized.Moreover,the presence of other waste metals in the leachate facilitated multi-heteroatom doping during synthesis.Interestingly,the introduction of various dopants into CoO_(x)induced oxygen vacancy formation,thereby enhancing the electrochemical properties of the CoO_(x)anode.As a result,compared with the phase-pure(undoped)CoO_(x)yolk–shell,the heteroatom-doped CoO_(x)yolk–shell exhibited robust cycling stability(602 mAh·g^(-1)for 200 cycles at 1 A·g^(-1))and excellent rate capability(210 mAh·g^(-1)at 10 A·g^(-1)).展开更多
文摘The development of metal-free carbon catalysts has garnered significant attention as a promising approach to address the challenges of sustainable catalysis,particularly in the replacement of toxic and environmentally hazardous mercury-based systems for the coal-based PVC industry.Within a decade of development,the catalytic performance of carbon catalysts has been improved greatly and even shows superiorities over metal catalysts in some cases,which have demonstrated great potential as sustainable alternatives to mercury catalysts.This review provides a comprehensive summary of the recent advancements in carbon catalysts for acetylene hydrochlorination.It encompasses a wide range of aspects,including the identification of active sites from heteroatom doping to intrinsic carbon defects,the various synthetic strategies employed,the reaction and deactivation mechanisms of carbon catalysts,and the current insights into the key challenges that are encountered on the journey from laboratory research to scalable commercialization within the field of carbon catalysts.The review offers foundational insights and practical guidelines for designing green carbon catalysts systems,not only for acetylene hydrochlorination but also for other heterogeneous catalytic reactions.
基金the National Natural Science Foundation of China (Nos.22375059, 22005133, 51922039 and52273174)Shenzhen Science and Technology Program (No.RCJC20200714114434015)+1 种基金Science and Technology Innovation Program of Hunan Province (No.2020RC5033)National Key Research and Development Program of China (No.2020YFC1807302) for financial support。
文摘While heteroatom doping serves as a powerful strategy for devising novel polycyclic aromatic hydrocarbons(PAHs), the further fine-tuning of optoelectronic properties via the precisely altering of doping patterns remains a challenge. Herein, by changing the doping positions of heteroatoms in a diindenopyrene skeleton, we report two isomeric boron, sulfur-embedded PAHs, named Anti-B_(2)S_(2) and Syn-B_(2)S_(2), as electron transporting semiconductors. Detailed structure-property relationship studies revealed that the varied heteroatom positions not only change their physicochemical properties, but also largely affect their solid-state packing modes and Lewis base-triggered photophysical responses. With their low-lying frontier molecular orbital levels, n-type characteristics with electron mobilities up to 1.5 × 10^(-3)cm^(2)V^(-1)s^(-1)were achieved in solution-processed organic field-effect transistors. Our work revealed the critical role of controlling heteroatom doping patterns for designing advanced PAHs.
基金financially supported by the Natural Science Foundation of Hebei Province (B02020208088, H2020206514, and B2021208074)the S&T Program of Hebei Province (20544401D, 20314401D, 206Z4406G, 21314402D, 21344601D, 22344402D, and 22373709D)the Research Start-up Funding at Hebei University of Science and Technology (1181381)
文摘Carbon dioxide(CO_(2))reduction into chemicals or fuels by electrocatalysis can eff ectively reduce greenhouse gas emissions and alleviate the energy crisis.Currently,CO_(2)electrocatalytic reduction(CO_(2)RR)has been considered as an ideal way to achieve“carbon neutrality.”In CO_(2)RR,the characteristics and properties of catalysts directly determine the reaction activity and selectivity of the catalytic process.Much attention has been paid to carbon-based catalysts because of their diversity,low cost,high availability,and high throughput.However,electrically neutral carbon atoms have no catalytic activity.Incorpo-rating heteroatoms has become an eff ective strategy to control the catalytic activity of carbon-based materials.The doped carbon-based catalysts reported at present show excellent catalytic performance and application potential in CO_(2)RR.Based on the type and quantity of heteroatoms doped into carbon-based catalysts,this review summarizes the performances and catalytic mechanisms of carbon-based materials doped with a single atom(including metal and without metal)and multi atoms(including metal and without metal)in CO_(2)RR and reveals prospects for developing CO_(2)electroreduction in the future.
基金supported by the National Key R&D Program of China(Nos.2022YFA1503100 and 2022YFA1503102)the National Natural Science Foundation of China(No.22273050)the Natural Science Foundation of Shandong Province(Nos.YDZX2021001 and ZR2022MB098).
文摘Replacing fossil fuels with fuel cells is a feasible way to reduce global energy shortages and environmental pollution.However,the oxygen reduction reaction(ORR)at the cathode has sluggish kinetics,which limits the development of fuel cells.It is significant to develop catalysts with high catalytic activity of ORR.The single-atom catalysts(SACs)of Pt supported on heteroatom-doped graphene are potential candidates for ORR.Here we studied the SACs of Pt with different heteroatoms doping and screened out Pt-C_(4) and Pt-C_(3)O_(1) structures with only 0.13 V overpotential for ORR.Meanwhile,it is found that B atoms doping could weaken the adsorption capacity of Pt,while N or O atoms doping could enhance it.This regularity was verified on Fe SACs.Through the electronic interaction analysis between Pt and adsorbate,we explained the mechanism of this regularity and further proposed a new descriptor named corrected d-band center(ε_(d-corr))to describe it.This descriptor is an appropriate reflection of the number of free electrons of the SACs,which could evaluate its adsorption capacity.Our work provides a purposeful regulatory strategy for the design of ORR catalysts.
基金supported by Royal Society Newton Advanced Fellowship(Nos.52061130218,NAF\R1\201127)the State Key Laboratory of Clean Energy Utilization Open Fund(No.ZJUCEU2019002).
文摘Activated carbon(AC)has attracted tremendous research interest as an electrode material for supercapacitors owing to its high specific surface area,high porosity,and low cost.However,AC-based supercapacitors suffer from limited rate performance and low power density,which mainly arise from their inherently low electrical conductivity and sluggish ion dynamics in the micropores.Here,we propose a simple yet effective strategy to address the aforementioned issue by nitrogen/fluorine doping and enlarging the micropore size.During the treatment,the decomposition products of NH4F react with the carbon atoms to dope the AC with nitrogen/fluorine and simultaneously enlarge the pores by etching.The treated AC shows a higher specific surface area of 1826 m2 g^(−1)(by~15%),more micropores with a diameter around 0.93 nm(by~33%),better wettability(contact angle decreased from 120°to 45°),and excellent electrical conductivity(96 S m^(−1))compared with untreated AC(39 S m^(−1)).The as-fabricated supercapacitors demonstrate excellent specific capacitance(26 F g^(−1)at 1 A g^(−1)),significantly reduced electrical resistance(by~50%),and improved rate performance(from 46.21 to 64.39%at current densities of 1 to 20 A g^(−1)).Moreover,the treated AC-based supercapacitor achieves a maximum energy density of 25 Wh kg^(−1)at 1000 W kg^(−1)and a maximum power density of 10,875 W kg^(−1)at 15 Wh kg^(−1),which clearly outperforms pristine AC-based supercapacitors.This synergistic treatment strategy provides an effective way to improve the rate performance and power density of AC-based supercapacitors.
基金supported by the National Natural Science Foundation of China(51873198)the Engineering and Physical Sciences Research Council(EPSRC,EP/V027433/1)the Royal Society(RGSR1211080)。
文摘Zinc-ion hybrid supercapacitors(ZHSs)are highly desirable for large-scale energy storage applications owing to the merits of high safety,low cost and ultra-long cycle life.The poor rate performance of cathodes,however,severely hinders their application.Herein,aqueous ZHSs with superior performance were fabricated by employing a series of ultrathin carbon nanobelts modified with B,N,O(CPTHBBx).The heteroatom doping can significantly modify the chemical behaviors of carbon frameworks,which could generate numerous active sites and accelerate the charge transport.The systematic investigation reveals that the B-N groups are active species for fast Zn-ion adsorption and desorption.As a result,the best-performed CPTHB-B2 exhibits an excellent electrochemical performance as cathodes in ZHSs,delivering a high specific capacitance of 415.3 F g^(−1) at 0.5 A g^(−1),a record high capacitance retention of 81%when increasing the current densities from 0.5 to 100 A g^(−1),an outstanding energy density of 131.9 W h kg^(−1) and an exceptionally high power density of 42.1 kW kg^(−1).Our work provides a new cathode design for ultrafast charging Zn-ion storage devices.
基金financially supported by the National Natural Science Foundation of China(22478432,22108306,22178388)Taishan Scholars Program of Shandong Province(tsqn201909065)+2 种基金Shandong Provincial Natural Science Foundation(ZR2024JQ004)Innovation Fund Project for Graduate Student of China University of Petroleum(East China)the Fundamental Research Funds for the Central Universities(No.25CX04020A)。
文摘The development of single atom catalysts(SACs)with asymmetric active sites by defect regulation provides an encourage potential for oxygen reduction reaction(ORR)and hydrogen evolution reaction(HER),but highly challenging.Herein,N-doped carbon(N-C)anchored atomically dispersed Ni-N_(3)site with proximity defects(Ni-N_(3)D)induced by Te atoms doping is reported.Benefitting from the inductive effect of proximity defect,the Ni-N_(3)D/Te-N-C catalyst performs excellent ORR and HER performance in alkaline and acid condition.Both in situ characterization and theoretical calculation reveal that the existence of proximity defect effect is conducive to lower rate-determining-step energy barrier of ORR and HER,thus accelerating the multielectron reaction kinetics.This work paves a novel strategy for constructing highactivity bifunctional SACs by defect engineering for development of sustainable energy.
文摘The Ni single-atom catalyst dispersed on nitrogen doped graphene support has attracted much interest due to the high selectivity in electro-catalyzing CO_(2)reduction to CO,yet the chemical inertness of the metal center renders it to exhibit electrochemical activity only under high overpotentials.Herein,we report P-and S-doped Ni single-atom catalysts,i.e.symmetric Ni_(1)/PN_(4)and asymmetric Ni1/SN_(3)C can exhibit high catalytic activity of CO_(2)reduction with stable potential windows.It is revealed that the key intermediate*COOH in CO_(2)electroreduction is stabilized by heteroatom doping,which stems from the upward shift of the axial d_(z2)orbital of the active metal Ni atom.Furthermore,we investigate the potential-dependent free energetics and dynamic properties at the electrochemical interface on the Ni1/SN3C catalyst using ab initio molecular dynamics simulations with a full explicit solvent model.Based on the potential-dependent microkinetic model,we predict that S-atom doped Ni SAC shifts the onset potential of CO_(2)electroreduction from–0.88 to–0.80 V vs.RHE,exhibiting better activity.Overall,this work provides an in-depth understanding of structure-activity relationships and atomic-level electrochemical interfaces of catalytic systems,and offers insights into the rational design of heteroatom-doped catalysts for targeted catalysis.
基金financially supported by the Natural Science Foundation of Shandong Province (No.ZR2022QE076)the National Natural Science Foundation of China (No.52202092)the Science and Technology Support Plan for Youth Innovation of Colleges and Universities of Shandong Province of China (No.2023KJ104)。
文摘Electrochemical CO_(2) reduction reaction(CO_(2)RR) into valuable formate provides a strategy for carbon neutrality.Bismuth(Bi) catalysts,attributed to their appropriate energy barrier of OCHO*intermediate,have demonstrated substantial potential for the advancement of electrocatalytic CO_(2) reduction to formate.However,due to the weak bonding of protons(H^(*)) of Bi,the available protonate of CO_(2) on Bi is insufficient,which limits the formation of OCHO^(*).Prediction by theoretical calculation,chlorine doping can effectively promote the dissociation of H_(2)O and thus achieve effective proton supply.We prepare chlorine-doped Bi(Cl-Bi) via an electrochemical conversion strategy for electroreduction of CO_(2) .An obvious improvement of faradaic efficiency(FE) of formate(96.7% at-0.95 V vs.RHE) can be achieved on Cl-Bi,higher than that of Bi(89.4%).Meanwhile,Cl-Bi has the highest formate production rate of 275 μmol h^(-1)cm^(-2)at-0.95 V vs.RHE,which is 1.2 times higher than that of Bi(224 μmol h^(-1)cm^(-2)).In situ characterizations and kinetic analysis reveal that chlorine doping promotes the activation of H_(2)O and supply sufficient protons to promote the protonation of CO_(2) to OCHO^(*),which is consistent with theoretical calculation.The study presents an effective strategy for rational design of highly efficient electrocatalysts to promote green chemical production.
基金financially supported by the National Natural Science Foundation of China(Nos.21671170,21673203,21805136 and 21201010)the Natural Science Foundation of Jiangsu Province(No.BK20170999)+2 种基金Program for New Century Excellent Talents of the University in China(No.NCET-13-0645)the Six Talent Plan(No.2015-XCL-030)Priority Academic Program Development of Jiangsu Higher Education Institutions。
文摘Lithium-sulfur batteries(LSBs)have received much concern as emerging high-power energy storage system.Nevertheless,the low conductivity of sulfur and poly sulfide shuttle results in low rate capability and rapid capacity decay,which seriously limit its commercial application.Here,facile,sustainable and cost-effective strategy for preparing heteroatom-doped porous activated carbon(PAC)derived from biomass palm kernel shell(PKS)was developed for high-performance LSB applications.The presence of N,P and S heteroatoms with modification of the surface polarity brings about large amounts of active sites and improved adsorption property compared to those of common carbon materials.The PAC sample possesses desirable specific surface area(SSA)(2760 m2·g-1)as well as pore volume(1.6 cm3·g-1).Besides,the good electrical conductivity of PAC endows the material with excellent rate performance.The PAC-S electrode with a 60%of sulfur loading has a desirable first discharge capacity(1045 mAh·g1,200 mA·g-1)with superb discharge capacity(869.8 mAh·g-1,100 th cycle)and cyclability(312.6 mAh·g-1,800 mA·g-1,1000 th cycle),which can be mainly ascribed to its unique porous properties and the good conductivity of PAC.
基金supported by the National Natural Science Foundation of China(22108306,22109090)the Taishan Scholars Program of Shandong Province(tsqn201909065)the Shandong Provincial Natural Science Foundation(ZR2021YQ15,ZR2020QB174)。
文摘Developing high-efficiency multifunctional nanomaterials is promising for wide p H hydrogen evolution reaction(HER) and energy storage but still challenging. Herein, a novel in-situ doping-induced lattice strain strategy of NiCoP/S nanocrystals(NCs) was proposed through using seed crystal conversion approach with NiCo_(2)S_(4) spinel as precursor. The small amount of S atoms in NiCoP/S NCs perturbed the local electronic structure, leading to the atomic position shift of the nearest neighbor in the protocell and the nanoscale lattice strain, which optimized the H* adsorption free energy and activated H_(2)O molecules, resulting the dramatically elevated HER performance within a wide p H range. Especially, the NiCoP/S NCs displayed better HER electrocatalytic activity than comical 20% Pt/C at high current density in 1 M KOH and natural seawater: it only needed 266 m V vs. reversible hydrogen electrode(RHE) and660 m V vs. RHE to arrive the current density of 350 m A cm^(-2) in 1 M KOH and natural seawater, indicating the application prospect for industrial high current. Besides, NiCoP/S NCs also displayed excellent supercapacitor performance: it showed high specific capacity of 2229.9 F g^(-1) at 1 A g^(-1) and energy density of87.49 Wh kg^(-1), when assembled into an all-solid-state flexible device, exceeding performance of most transition metal phosphides. This work provides new insights into the regulation in electronic structure and lattice strain for electrocatalytic and energy storage applications.
基金financially supported by the National Natural Science Foundation of China (Nos. 22179123 and 21471139)Shandong Provincial Natural Science Foundation, China (No. ZR2020ME038)+1 种基金Shandong Provincial Key R&D Plan and the Public Welfare Special Program, China (No. 2019GGX102038)the Fundamental Research Funds for the Central Universities (No. 201941010)
文摘Zinc ion capacitors(ZICs)have drawn increas-ing interest in energy storage devices because of their economic benefits,high safety,and long cycling life.Nevertheless,the lack of high-performance cathodes for ZICs remains a key challenge.Here,we fabricated B,N co-doped porous carbon(BN-C)via a salt template strategy.The aqueous ZICs assembled from BN-C cathode delivered a high capacity of 190.2 mAh·g^(-1)and a remarkable energy density of 105.1 Wh·kg^(-1).Moreover,systematic charac-terization verifies that B/N dual-doping promotes the physical adsorption/desorption kinetics of anion and the chemical absorption/desorption kinetics of Zn^(2+),thus improving the electrochemical performance of ZICs.In addition,the quasi-solid-state pouch-type battery exhibited excellent electrochemical durability and mechanical flexi-bility,demonstrating its vast application potential as a flexible power source.Overall,this research not only pre-sents a reasonable approach to the large-scale production of carbon cathode materials with excellent electrochemical performance but also strengthens the essential recognition of the charge storage mechanism of heteroatoms-doped carbon materials.
基金supported by the National Natural Science Foundation of China(22179065,22111530112,21875118)the Tianjin Graduate Research and Innovation Project(2022BKY018)the Ph.D.Candidate Research Innovation Fund of NKU School of Materials Science and Engineering.
文摘Hydrazine-assisted water electrolysis is a promising energy conversion technology for highly efficient hydrogen production.Rational design of bifunctional electrocatalysts,which can simultaneously accelerate hydrogen evolution reaction(HER)/hydrazine oxidation reaction(HzOR)kinetics,is the key step.Herein,we demonstrate the development of ultrathin P/Fe co-doped NiSe_(2) nanosheets supported on modified Ni foam(P/Fe-NiSe_(2)) synthesized through a facile electrodeposition process and subsequent heat treatment.Based on electrochemical measurements,characterizations,and density functional theory calculations,a favorable“2+2”reaction mechanism with a two-step HER process and a two-step HzOR step was fully proved and the specific effect of P doping on HzOR kinetics was investigated.P/Fe-NiSe_(2) thus yields an impressive electrocatalytic performance,delivering a high current density of 100 mA cm^(−2) with potentials of−168 and 200 mV for HER and HzOR,respectively.Additionally,P/Fe-NiSe_(2) can work efficiently for hydrazine-assisted water electrolysis and Zn-Hydrazine(Zn-Hz)battery,making it promising for practical application.
基金supported by the National Natural Science Foundation of China (No. 22165028)the Nature Science Foundation of Gansu Province (No. 20JR10RA108)the Innovation Fund of Gansu Universities (No. 2020A-013)。
文摘Constructing anodes with fast ions/electrons transfer paths is an effective strategy to achieve high-performance sodium ion batteries(SIBs)/potassium ion batteries(PIBs). Amorphous carbon is a promising candidate anode for SIBs/PIBs owing to its disordered carbon layers, abundant defects/pores, and lowcost resources. However, the larger radius of Na^(+)/K^(+) leading to depressed kinetics and poor cycling performance, impeding their further applications. Herein, we propose an efficient strategy to construct of nitrogen, sulfur co-doped hollow carbon nanospheres(NS-HCS) involving an in situ growth of polydopamine on nano-Ni(OH)2template with subsequent sulfur doping process. During the formation process, the produced Ni nanospheres play as the hard template and catalyst for the formation of hollow carbon nanosphere with partially graphite microcrystalline structure, while the sulfur doping process can enlarge the interlayer space and create more defects on the surface of carbon nanospheres, thus synchronous improve the Na^(+)/K^(+) insertion and adsorption ability in NS-HCS. With the synergistic control of the enlarged interlayer spacing, high content of pyridinic N/pyrrolic N and graphitization, a hybrid storage mechanism facilitates the transport kinetics and endows the NS-HCS electrode with high capacities and good cycling stability in SIBs and PIB. Benefit from the multiple effects, NS-HCS exhibits the improved capacity of 274.8 m Ah/g at 0.1 A/g and excellent cycling stability of 149.5 m Ah/g after 5000 cycles at2.5A/g in SIBs, as well as good potassium ion storage behavior with a high capacity retention of 76.5%after 700 cycles at 1.0 A/g, demonstrating the potential applications of NS-HCS for high-performance SIBs and PIBs.
基金supported by the Doctor Foundation of Bingtuan (No.2014BB004)National Natural Science Foundation of China (U130329)+1 种基金the Program for Changjiang Scholars, Innovative Research Team in University (No. IRT_15R46)the Program of Science and Technology Innovation Team in Bingtuan (No. 2015BD003)
文摘Banana peel-derived porous carbon(BPPC) was prepared from banana peel and used as an adsorbent for methyl orange(MO) wastewater removal. BPPC-MO50 is a N,S-doped BPPC obtained via secondary carbonization. The BPPC-MO50 exhibited a high specific surface area of1774.3 m^2/g. Heteroatom-doped porous carbon(PC) was successfully synthesized from the BPPC absorbed MO at high temperature and used for oxygen reduction. The BPPC-MO50 displayed the highest ORR onset potential among all carbon-based electrocatalysts, i.e., 0.93 V vs.reversible hydrogen electrode(RHE). This is the first report to describe porous carbon-activated materials from agriculture and forestry waste that is used for adsorption of dyes from wastewater via an enhanced heteroatom(N,S) content. These results may contribute to the sustainable development of dye wastewater treatment by transforming saturated PC into an effective material and has potential applications in fuel cells or as energy sources.
基金financially supported by the National Natural Science Foundation of China(21972068,21875112,22072067,21878047,22075290 and 21676056)the Qing Lan Project of Jiangsu Province(1107040167)+3 种基金the Postgraduate Research&Practice Innovation Program of Jiangsu Province(KYCX20_0121)the China Scholarship Council(CSC,202006090294)the Fundamental Research Funds for the Central Universities(3207042101D)A Project Funded by the Priority Academic Program Development of Jiangsu Higher Education Institutions(PAPD)(1107047002)。
文摘The search for non-precious and efficient electrocatalysts towards the oxygen evolution reaction(OER)is of vital importance for the future advancement of multifarious renewable energy conversion/storage technologies.Electronic modulation via heteroatom doping is recognized as one of the most forceful leverages to enhance the electrocatalytic activity.Herein,we demonstrate a delicate strategy for the in-situ confinement of S-doped Ni O nanoparticles into N-doped carbon nanotube/nanofiber-coupled hierarchical branched superstructures(labeled as S-Ni O@N-C NT/NFs).The developed strategy simultaneously combines enhanced thermodynamics via electronic regulation with accelerated kinetics via nanoarchitectonics.The S-doping into Ni O lattice and the 1 D/1 D-integrated hierarchical branched carbon substrate confer the resultant S-Ni O@N-C NT/NFs with regulated electronic configuration,enriched oxygen vacancies,convenient mass diffusion pathways and superior architectural robustness.Thereby,the SNi O@N-C NT/NFs display outstanding OER properties with an overpotential of 277 m V at 10 m A cm^(-2)and impressive long-term durability in KOH medium.Density functional theory(DFT)calculations further corroborate that introducing S-dopant significantly enhances the interaction with key oxygenate intermediates and narrow the band gap.More encouragingly,a rechargeable Zn-air battery using an air-cathode of Pt/C+S-Ni O@N-C NT/NFs exhibits a lower charge voltage and preferable cycling stability in comparison with the commercial Pt/C+Ru O_(2)counterpart.This study highlighting the concurrent consideration of electronic regulation,architectural design and nanocarbon hybridization may shed light on the future exploration of economical and efficient electrocatalysts.
基金supported by the National Natural Science Foundation of China(21503051,21563007)the Natural Science Foundation of Guangxi Province(2019GXNSFFA245016,2018GXNSFAA138108)。
文摘Modulate the electronic structure and surface energy by nanostructure and heteroatom doping is an efficient strategy to improve electrocatalytic activity of hydrogen evolution reaction(HER).Herein,nickel incorporated WP_(2) self-supporting nanosheet arrays cathode was synthesized on carbon cloth(Ni-WP_(2) NS/CC)by in-situ phosphating reduction of the Ni-doped WO3.It shows that heteroatom doping and the three-dimensional(3D)nanosheet arrays morphology both facilitate to reduce the interfacial transfer resistance and increase electrochemical-active surface areas,which effectively improve electrocatalytic hydrogen evolution reaction(HER)activity.The optimized catalyst,1%Ni-WP_(2) NS/CC,exhibits an outstanding electrocatalytic performance with an overpotential of 110 m V at 10 m A cm^(-2) and a Tafel slope of 65 m V dec^(-1) in the acid solution.DFT calculations further demonstrate the nickel doping can adjust the intrinsic structure of electronics,lower the Gibbs free energy of adsorption of hydrogen(DGH*),and effectively improve the HER performance.
基金financial support from the Nankai UniversityNational Science Foundation of China(No.21875119)+1 种基金Natural Science Foundation of Tianjin(19JCYBJC17500)the open fund of the key laboratory of advanced functional polymer materials,the ministry of education(Nankai University,KLFPM202001)。
文摘Electrocatalysts play a crucial role in the development of renewable energy conversion and storage nanotechnologies.The unique advantages of heteroatom-doped porous carbon-supported single-atom electrocatalysts(SAC-HDPCs)are clear.These SAC-HDPCs exhibit outstanding activity,selectivity and stability due to their distinct electronic structure,satisfactory conductivity,controllable porosity and heteroatomdoping effect.Rapid and significant developments involving the synthesis,characterization,and structure-property-function relationship of SAC-HDPCs have been made in recent years.In this review,we describe recent research efforts involving advanced(in situ)characterization techniques,innovative synthetic strategies,and electrochemical energy conversion examples of SAC-HDPCs.The electrocatalytic performance of SAC-HDPCs is further considered at an atomic level,and the mechanisms underlying this performance are also discussed in detail.We expect that these analyses and deductions will be useful for the design of new materials and may help to establish a foundation for the design of future SAC-HDPCs.
基金supported by the funding from Qilu University of Technology(Shandong Academy of Sciences)the Science and Technology Development Fund,Macao SAR(File No.191/2017/A3,041/2019/A1,046/2019/AFJ,0021/2019/AIR)+2 种基金the National Natural Science Foundation of China(Grant No.51972180)the Multi-Year Research Grants(Nos.MYRG2017-00216-FST and MYRG2018-00192-IAPME)from the Research Services and Knowledge Transfer Office at the University of MacaoUEA funding.
文摘CoPS nanoparticles encapsulated with S,P,N tri-doped carbon material(SPNC)were proposed as bifunctional electrocatalyst of oxygen evolution reaction(OER)and oxygen reduction reaction(ORR)derived from zeolitic imidazolate framework-67.Density functional theory calculations consistently revealed that P element in CoPS@SPNC improves the electrical conductivity and reduces OH^(*)hydrogenation energy barrier on Co sites,thereby facilitating the overall ORR/OER activities.A flexible Zn–air battery with CoPS@SPNC delivered an overpotential of 0.49 V,an energy efficiency above 80%,and a discharge voltage of 1.29 V at 2 mA cm^(-2) for 80 h.
基金financially supported by the National Research Foundation of Korea(NRF)from the Korea Government(MEST,No.NRF-2022R1F1A1070886MSIT,No.RS2023-00217581)the Commercialization Promotion Agency for R&D Outcomes(COMPA)from the Korea Government(MEST,No.1711175258)。
文摘Heteroatom-doped transition metal oxides have attracted great attention as advanced anode materials for lithium-ion batteries due to their high theoretical capacity and superior properties.However,the limited resource availability has led to a substantial rise in prices for valuable metals such as Ni and Co,posing a significant challenge for their application.To address this issue,recycling of these metals from waste materials have gained prominence,and particularly the recovery of Co has been mostly focused on its economic benefits.Herein,we introduced a novel recycling strategy for fabrication of heteroatomdoped CoO_(x)(comprising mainly Co_(3)O_(4)with a minor CoO phase)anode with a yolk–shell structure for lithium-ion batteries,by separating Co from cemented tungsten carbide waste.By employing a simple leaching process and subsequent spray pyrolysis,the yolk–shell structured microsphere comprising CoO_(x)was successfully synthesized.Moreover,the presence of other waste metals in the leachate facilitated multi-heteroatom doping during synthesis.Interestingly,the introduction of various dopants into CoO_(x)induced oxygen vacancy formation,thereby enhancing the electrochemical properties of the CoO_(x)anode.As a result,compared with the phase-pure(undoped)CoO_(x)yolk–shell,the heteroatom-doped CoO_(x)yolk–shell exhibited robust cycling stability(602 mAh·g^(-1)for 200 cycles at 1 A·g^(-1))and excellent rate capability(210 mAh·g^(-1)at 10 A·g^(-1)).
