Doped calcium carbonate-phosphate is a biocompatible material that influence actively on the osteogenesis, bone regenerate, strengthening of bone and dental tissues including through the skin. A mechanism of the synth...Doped calcium carbonate-phosphate is a biocompatible material that influence actively on the osteogenesis, bone regenerate, strengthening of bone and dental tissues including through the skin. A mechanism of the synthesis reactions of doped nanocrystalline calcium carbonate-phosphate an oscillating type of model for these reactions is proposed. The results indicate that the synthesis involves the formation of hydroxy carbonate complexes from the three calcium carbonate polymorphs (calcite, vaterite, and aragonite) in a solution of ammonium chloride and ammonium carbonate, followed by reaction with orthophosphoric acid. The formation of nanocrystalline calcium carbonate-phosphate doped with Fe2+, Mg2+, Zn2+, K+, Si4+, and Mn2+, has been studied by X-ray diffraction, IR spectroscopy, differential thermal analysis, and energy dispersive X-ray fluorescence analysis. This ensures the preparation of a bioactive material based on octacalcium hydrogen phosphate, and calcium chloride hydroxide phosphates containing cation vacancies. Particle-size analysis data show that the materials contain nanoparticles down to 10 nm in size. Heat treatment of the doped calcium carbonate phosphates produces calcium hydroxyapatite containing cation vacancies, which can be used as a bioactive ceramic.展开更多
Graphite as a promising anode candidate of K-ion batteries(KIBs)has been increasingly studied currently,but corresponding rate performance and cycling stability are usually inferior to amorphous carbon materials.To pr...Graphite as a promising anode candidate of K-ion batteries(KIBs)has been increasingly studied currently,but corresponding rate performance and cycling stability are usually inferior to amorphous carbon materials.To protect the layer structure and further boost performance,tempura-like carbon/carbon nanocomposite of graphite@pitch-derived S-doped carbon(G@PSC)is designed and prepared by a facile and low-temperature modified molten salt method.This robust encapsulation structure makes their respective advantages complementary to each other,showing mutual promotion of electrochemical performances caused by synergy effect.As a result,the G@PSC electrode is applied in KIBs,delivering impressive rate capabilities(465,408,370,332,290,and 227 m A h g^(-1)at 0.05,0.2,0.5,1,2,and 5 A g^(-1))and ultralong cyclic stability(163 m A g^(-1)remaining even after 8000 cycles at 2 A g^(-1)).On basis of ex-situ studies,the sectionalized K-storage mechanism with adsorption(pseudocapacitance caused by S doping)-intercalation(pitch-derived carbon and graphite)pattern is revealed.Moreover,the exact insights into remarkable rate performances are taken by electrochemical kinetics tests and density functional theory calculation.In a word,this study adopts a facile method to synthesize high-performance carbon/carbon nanocomposite and is of practical significance for development of carbonaceous anode in KIBs.展开更多
Carbonaceous materials are regarded as a promising anode material for potassium ion batteries(PIBs)due to their high electronic conductivity, abundant resources and low cost. However, relatively low storage capacity a...Carbonaceous materials are regarded as a promising anode material for potassium ion batteries(PIBs)due to their high electronic conductivity, abundant resources and low cost. However, relatively low storage capacity and structural instability still hinder their practical application. Herein, high sulfur-doped hard carbon(SHC-3) with a sulfur up to 27.05 at% is synthesized from polystyrene and sulfur as precursors. As an anode for PIBs, the SHC-3 delivers a superb cycling stability and rate performance(298.1 mAh g^(-1)at 100 mA g^(-1) for 1000 cycles, a capacity retention of 95.2%;220.2 mAh g^(-1)at 500 mA g^(-1) after 5200 cycles). The potassium storage of SHC-3 exhibits excellent cyclic stability at both low and high rates.Structure and kinetic studies demonstrate that the larger interlayer spacing(0.382 nm) of the SHC-3 accelerates the diffusion of potassium ions and effectively alleviates the volume expansion, and thus maintains the structure stability during the process of potassization/de-potassization. Meanwhile, the density functional theory calculation shows that the doped sulfur atoms provide abundant active sites for the adsorption of potassium ions, thereby increasing the reversible capacity of PIBs. This work provides a new scheme for the design of carbonaceous anode materials with high capacity and long cycle life.展开更多
Integrating the merits of long lifespan and excellent energy as well as power densities,potassium-ion hybrid capacitors(PIHCs)exhibit great prospects for future energy storage devices.To boost comprehensive performanc...Integrating the merits of long lifespan and excellent energy as well as power densities,potassium-ion hybrid capacitors(PIHCs)exhibit great prospects for future energy storage devices.To boost comprehensive performance of PIHCs,heteroatom-doping and morphology-tuning as two comprehensive strategies have been devoted to designing uniquely structural carbon-based materials with favorable advantages.An ideal strategy for simultaneous atomic doping and structural regulation is expected to be developed.Herein,we propose a novel"Killing Two Birds with One Stone"strategy to prepare a tri-elements doped hollow carbon sphere(TED-HCS)as PIHCs anodes,that is,a single template of spherical CoP particles is rationally adopted,which not only provides both a P source for heteroatom-doping but also acts as a selfsacrificial template for hollow-structure engineering.The multifunctional TED-HCS presents a high capacity of 473.0 mAh g^(-1) and excellent rate performance of 212.5 mAh g^(-1) at 5.0 A g^(-1).Remarkably,the as-assembled PIHCs show outstanding energy/power density(40.4 Wh kg^(-1)/10500 W kg^(-1))and remain high-capacity retention of 89.15%even cycling 12,000 times.The"Killing Two Birds with One Stone"strategy offers new insight into the search for the preparation of carbon-based materials with multi-elements doping and specific morphology structure.展开更多
The key to construct high-energy supercapacitors is to maximize the capacitance of electrode and the voltage of the device. Realizing this purpose by utilizing sustainable and low-cost resources is still a big challen...The key to construct high-energy supercapacitors is to maximize the capacitance of electrode and the voltage of the device. Realizing this purpose by utilizing sustainable and low-cost resources is still a big challenge. Herein, N, B co-doped carbon nanosheets are obtained through the proposed dual-template assisted approach by using methyl cellulose as the precursor. Due to the synergistic effects form the high surface area with the hierarchical porous structure, N/B dual doping, and a high degree of graphitization, the resultant carbon electrode exhibits a high capacitance of 572 F g^(-1)at 0.5 A g^(-1)and retains 281 F g^(-1)at 50 A g^(-1)in an acidic electrolyte. Furthermore, the symmetric device assembled using bacterial cellulose-based gel polymer electrolyte can deliver high energy density of 43 W h kg^(-1)and excellent cyclability with 97.8% capacity retention after 20 000 cycles in “water in salt” electrolyte. This work successfully realizes the fabrication of high-performance allcellulose-based quasi-solid-state supercapacitors, which brings a cost-effective insight into jointly designing electrodes and electrolytes for supporting highly efficient energy storage.展开更多
Solid‐state Zn–air batteries(ZABs)hold great potential for application in wearable and flexible electronics.However,further commercialization of current ZABs is still limited by the poor stability and low energy eff...Solid‐state Zn–air batteries(ZABs)hold great potential for application in wearable and flexible electronics.However,further commercialization of current ZABs is still limited by the poor stability and low energy efficiency.It is,thus,crucial to develop efficient catalysts as well as optimize the solid electrolyte system to unveil potential of the ZAB technology.Due to the low cost and versatility in tailoring the structures and properties,carbon materials have been extensively used as the conductive substrates,catalytic air electrodes,and important components in the electrolytes for the solid‐state ZABs.Within this context,we discuss the challenges facing current solid‐state ZABs and summarize the strategies developed to modify properties of carbon‐based electrodes and electrolytes.We highlight the metal−organic framework/covalent organic framework‐based electrodes,heteroatom‐doped carbon,and the composites formed of carbon with metal oxides/sulfides/phosphides.We also briefly discuss the progress of graphene oxide‐based solid electrolyte.展开更多
Biomass-derived carbon materials have aroused widespread concern as host material of sulfur to enhance electrochemical performances for lithium–sulfur batteries. Herein, goat hair, as a low-cost and eco-friendly prec...Biomass-derived carbon materials have aroused widespread concern as host material of sulfur to enhance electrochemical performances for lithium–sulfur batteries. Herein, goat hair, as a low-cost and eco-friendly precursor, is employed to fabricate cauliflower-like in-situ nitrogen, oxygen and phosphorus tri-doped porous biomass carbon(NOPC) by a facile activation with H_3PO_4 and carbonization process.The morphology and microstructure of NOPC can be readily tuned by altering pyrolysis temperature. The as-prepared NOPC matrix material carbonized at 600 °C possesses 3D hierarchical porous structure, high specific surface area(535.352 m^2 g^(-1)), and appropriate pore size and pore size distribution. Encapsulating sulfur into the NOPC depends on a stem-melting technology as cathode materials of Li–S batteries. Due to the synergistic effect of special physical structure and inherent tri-doping of N, O and P, electrons and ions transfer and utilization of active sulfur in the materials are improved, and the shuttle behaviors of soluble lithium polysulfides are also mitigated. Consequently, the S/NOPC-600 composite exhibits excellent electrochemical performance, giving a high initial discharge capacity of 1185 mA h g^(-1) at 0.05 C and maintaining a relatively considerable capacity of 489 m A h g^(-1) at 0.2 C after 300 cycles. Our work shows that a promising candidate for cathode material of Li–S batteries can be synthesized using low-cost and renewable biomass materials by a facile process.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
The use of carbon‐based materials is an appealing strategy to solve the issue of excessive CO_(2) emis‐sions.In particular,metal‐free nitrogen‐doped carbon materials(mf‐NCs)have the advantages of convenient synth...The use of carbon‐based materials is an appealing strategy to solve the issue of excessive CO_(2) emis‐sions.In particular,metal‐free nitrogen‐doped carbon materials(mf‐NCs)have the advantages of convenient synthesis,cost‐effectiveness,and high conductivity and are ideal electrocatalysts for the CO_(2) reduction reaction(CO_(2)RR).However,the unclear identification of the active N sites and the low intrinsic activity of mf‐NCs hinder the further development of high‐performance CO_(2)RR electrocat‐alysts.Achieving precise control over the synthesis of mf‐NC catalysts with well‐defined active N‐species sites is still challenging.To this end,we adopted a facile synthesis method to construct a set of mf‐NCs as robust catalysts for CO_(2)RR.The resulting best‐performing catalyst obtained a Far‐adaic efficiency of CO of approximately 90%at−0.55 V(vs.reversible hydrogen electrode)and good stability.The electrocatalytic performance and in situ attenuated total reflectance surface‐enhanced infrared absorption spectroscopy measurements collectively revealed that graphitic and pyridinic N can synergistically adsorb CO_(2) and H_(2)O and thus promote CO_(2) activation and protonation.展开更多
The nitrogen doped graphene was synthesized by hydrothermal route utilizing 2-Chloroethylamine hydrochloride as nitrogen precursor in the presence of graphene oxide (GO). Nitrogen-doped graphene material is developed ...The nitrogen doped graphene was synthesized by hydrothermal route utilizing 2-Chloroethylamine hydrochloride as nitrogen precursor in the presence of graphene oxide (GO). Nitrogen-doped graphene material is developed for its application in hydrogen storage at room temperature. Nitrogen doped graphene layered material shows ~1.5 wt% hydrogen storage capacity achieved at room temperature and 90 bar pressure.展开更多
A variety of distinctive techniques have been developed to produce graphene sheets and their functionalized subsidiaries or composites. The production of graphene sheets by oxidative exfoliation of graphite can be a s...A variety of distinctive techniques have been developed to produce graphene sheets and their functionalized subsidiaries or composites. The production of graphene sheets by oxidative exfoliation of graphite can be a suitable route for the preparation of high volumes of graphene derivatives. P-substituted graphene material is developed for its application in hydrogen sorption in room temperature. Phosphorous doped graphene material with multi-layers of graphene shows a nearly ~2.2 wt% hydrogen sorption capacity at 298 K and 100 bar. This value is higher than that for reduced graphene oxide (RGO without phosphorous).展开更多
This paper presents a new process for synthesizing a kind of nitrogen- doped carbon nanotubes (N-CNTs) with primarily a ‘graphite-like’ structure at N substitutions from flames using n-propylamine and n-butylamine a...This paper presents a new process for synthesizing a kind of nitrogen- doped carbon nanotubes (N-CNTs) with primarily a ‘graphite-like’ structure at N substitutions from flames using n-propylamine and n-butylamine as fuels. When the N-CNTs are used as the supercapacitor electrode materials, they exhibit a much larger capacitance than the regular carbon nanotubes (CNTs). It is proposed that the high proportional ‘graphite-like’ N dopant in the as-grown N-CNTs improves their surface chemical activity and conductivity and then results in a desirable performance for electro-chemical capacitors.展开更多
Activating MoS_(2) with atomic metal doping is promising to harvest desirable Pt-matched hydrogen evolution reaction(HER)catalytic performance.Herein,we developed an efficient method to access edgerich lattice-distort...Activating MoS_(2) with atomic metal doping is promising to harvest desirable Pt-matched hydrogen evolution reaction(HER)catalytic performance.Herein,we developed an efficient method to access edgerich lattice-distorted MoS_(2) for highly efficient HER via in-situ sulphuration of atomic Co/Mo species that were well-dispersed in a formamide-derived N-doped carbonaceous(f-NC)substrate.Apart from others,pre-embedding Co/Mo species in f-NC controls the release of metal sources upon annealing in S vapor,grafting the as-made MoS_(2) with merits of short-range crystallinity,distorted lattices,rich defects,and more edges exposed.The content of atomic Co species embedded in MoS_(2) reaches up to 2.85 at.%,and its atomic dispersion has been systematically confirmed by using XRD,HRTEM,XPS,and XAS characterizations.The Co-doped MoS_(2) sample exhibits excellent HER activity,achieving overpotentials of 67 and155 m V at j=10 m A cm^(-2) in 1.0 M KOH and 0.5 M H_(2)SO_(4),respectively.Density functional theory simulations suggest that,compared with free-doping MoS_(2),the edged Co doping is responsible for the significantly improved HER activity.Our method,in addition to providing reliable Pt-matched HER catalysts,may also inspire the general synthesis of edge-rich metal-doped metal chalcogenide for a wide range of energy conversion applications.展开更多
Hydrogen is recognized as a promising energy scours in the close future.Online hydrogen preparation from formic acid under mild reaction conditions causes extensive interests.Mo_(2)C and metal(Fe,Ni,Co,K)doped Mo_(2)C...Hydrogen is recognized as a promising energy scours in the close future.Online hydrogen preparation from formic acid under mild reaction conditions causes extensive interests.Mo_(2)C and metal(Fe,Ni,Co,K)doped Mo_(2)C on granular activated carbon(GAC)were prepared and used as heterogeneous catalysts for H2 generation from formic acid on a fixed bed reactor at 100–250°C.The formic acid conversions on doped Mo_(2)C-Me/GAC are clearly improved,especially at lower reaction temperatures.Co doping presents outstanding effect on H2 selectivity and conversion rate compared to Ni and Fe.A 56.3%formic acid conversion was reached on Mo_(2)C-Co/GAC at 100°C,which triples that on Mo_(2)C/GAC at the same temperature.At 150°C,a high formic acid conversion over 90%was reached on Mo_(2)C-Co/GAC.These long lifetime catalysts with no precious metal provide a low cost route to hydrogen production from formic acid.展开更多
The unique structural features of hard carbon(HC)make it a promising anode candidate for sodium-ion batteries(SIB).However,traditional methods of preparing HC require special equipment,long reaction times,and large en...The unique structural features of hard carbon(HC)make it a promising anode candidate for sodium-ion batteries(SIB).However,traditional methods of preparing HC require special equipment,long reaction times,and large energy consumption,resulting in low throughputs and efficiency.In our contribution,a novel synthesis method is proposed,involving the formation of HC nanosheets(NS-CNs)within minutes by creating an anoxic environment through flame combustion and further introducing sulfur and nitrogen sources to achieve heteroatom doping.The effect of heterogeneous element doping on the microstructure of HC is quantitatively analyzed by high-resolution transmission electron microscopy and image processing technology.Combined with density functional theory calculation,it is verified that the functionalized HC exhibits stronger Na^(+)adsorption ability,electron gain ability,and Na^(+) migration ability.As a result,NS-CNs as SIB anodes provide an ultrahigh reversible capacity of 542.7mAh g^(-1) at 0.1Ag^(-1),and excellent rate performance with a reversible capacity of 236.4mAh g^(-1) at 2Ag^(-1) after 1200 cycles.Furthermore,full cell assembled with NS-CNs as the can present 230mAh g^(-1) at 0.5Ag^(-1) after 150 cycles.Finally,in/ex situ techniques confirm that the excellent sodium storage properties of NS-CNs are due to the construction of abundant active sites based on the novel synthesis method for realizing the reversible adsorption of Na^(+).This work provides a novel strategy to develop novel carbons and gives deep insights for the further investigation of facile preparation methods to develop high-performance carbon anodes for alkali-ion batteries.展开更多
In this work, nitrogen doped clews-like carbon materials were successfully fabricated through hydrothermal polymerization method, followed by post treatment that integrated the carbonization,activation and post-nitrog...In this work, nitrogen doped clews-like carbon materials were successfully fabricated through hydrothermal polymerization method, followed by post treatment that integrated the carbonization,activation and post-nitrogen doping into one process. This preparation method can form particular hierarchical porous structure without using any sacrificial templates. The experimental results show that the nitrogen doped clews-like hierarchical porous carbon materials possess a relatively high specific surface area of 815 m^2/g with the nitrogen content of 10.58 at%. The electrochemical properties show that the resulting sample delivers 258 F/g at a 0.5 A/g and excellent capacity retention of 79% at 20 A/g. After conducting 10,000 charge-discharge cycles at 10 A/g, the capacitance retention of 98.3% is achieved.These intriguing results demonstrate that the obtained nitrogen doped clews-like carbon materials will be promising electrode materials for supercapacitor and other energy storage devices.展开更多
In recent years, especially when there is increasing concern about the safety issue of lithium-ion batteries (LIBs), aqueous Zn-ion batteries (ZIBs) have been getting a lot of attention because of their cost-effective...In recent years, especially when there is increasing concern about the safety issue of lithium-ion batteries (LIBs), aqueous Zn-ion batteries (ZIBs) have been getting a lot of attention because of their cost-effectiveness, materials abundance, high safety, and ecological friendliness. Their working voltage and specific capacity are mainly determined by their cathode materials. Vanadium oxides are promising cathode materials for aqueous ZIBs owing to their low cost, abundant resources, and multivalence. However, vanadium oxide cathodes still suffer from unsatisfactory capacity, poor stability, and low electrical conductivity. In this work, cascading V_(2)O_(3)/nitrogen doped carbon (V_(2)O_(3)/NC) hybrid nanosheets are prepared for high-performance aqueous ZIBs by pyrolyzing pentyl viologen dibromide (PV) intercalated V_(2)O5 nanosheets. The unique structure features of V_(2)O_(3)/NC nanosheets, including thin sheet-like morphology, small crystalline V_(2)O_(3) nanoparticles, and conductive NC layers, endow V_(2)O_(3)/NC with superior performance compared to most of the reported vanadium oxide cathode materials for aqueous ZIBs. The V_(2)O_(3)/NC cathode exhibits the discharge capacity of 405 mAh/g at 0.5 A/g, excellent rate capability (159 mAh/g at 20 A/g), and outstanding cycling stability with 90% capacity retention over 4000 cycles at 20 A/g.展开更多
Nitrogen-doped porous carbon materials(NPCs) have been successfully fabricated by a simple one-step pyrolysis of diethylenetriaminepentaacetic acid(DTPA) in the presence of KOH. The as-synthesized NPCs displayed a...Nitrogen-doped porous carbon materials(NPCs) have been successfully fabricated by a simple one-step pyrolysis of diethylenetriaminepentaacetic acid(DTPA) in the presence of KOH. The as-synthesized NPCs displayed a high specific surface area(3214 m;g;) and a well-defined porous structure when the annealing temperature reached 800 ℃, which showed superior electrochemical performance as supercapacitor electrode materials. Electrochemical tests showed that the NPCs achieved an impressive specific capacitance of 323 F g;at a current density of 0.5 A g;in 6 M KOH aqueous solution and an outstanding cycle stability, negligible specific capacitance decay after 5000 cycles at 10 A g;. This strategy offered a new insight into the preparation of novel carbon materials for the advanced energy storage devices, such as supercapacitors, fuel cells and lithium ion batteries.展开更多
Due to their superior fluorescence,phosphorescence,and catalytic capabilities,carbon dots(CDs),an emerging class of fluorescent carbon nanomaterials,have a wide range of potential applications.The properties of CDs ha...Due to their superior fluorescence,phosphorescence,and catalytic capabilities,carbon dots(CDs),an emerging class of fluorescent carbon nanomaterials,have a wide range of potential applications.The properties of CDs have recently been controlled extensively by heteroatom doping.Boron atoms have been effectively doped into the structure of CDs due to their similar size to carbon atoms and excellent electron-absorbing ability to further improve the performance of CDs.In this review,we summarize the research progress of boron-doped CDs in recent years from the aspects of doping strategies,effects of boron doping on different performances of CDs and applications.Starting from the two aspects of single boron doping and boron and other atom co-doping,from different precursor materials to different synthesis methods,the doping strategies of boron-doped CDs are reviewed in detail.Then,the effects of boron doping on the fluorescence,phosphorescence and catalytic performance of CDs and applications of boron-doped CDs in optical sensors,information encryption and anti-counterfeiting are discussed.Finally,we further provide a prospect towards the future development of boron-doped CDs.展开更多
Sulfur doped carbonaceous materials are promising anodes for potassium-ion batteries because of their ability to bridge active sites and induce C/S electron coupling,resulting in increased ion storage capacitance Howe...Sulfur doped carbonaceous materials are promising anodes for potassium-ion batteries because of their ability to bridge active sites and induce C/S electron coupling,resulting in increased ion storage capacitance However,the large potassium ions could cause significant volume expansion and structure collapse during operation in sulfur doped carbonaceous anodes,which lead to rapidly capacity sacrifice during long-term cycling.Nanopore design for anchoring sulfur atom in carbon skeleton is a novel way to alleviate the structure collapse and maintain the cycling stability.Therefore,this study developed a controlled nanopore and sulfur doped carbon sphere structure(S-NPHCSs).In potassium-ion batteries S-NPHCSs anode demonstrated exceptional performance with a high reversible capacity of 247 mAh·g^(–1)after 50 cycles at 0.2 A·g^(–1)and delivered a long cycle stability of 600 cycles at a high current density of 1.0 A·g^(–1).Interconnected nanopores and doped sulfur structure not only expand the accumulation space and offer ample active sites for diffusion and adsorption of potassium ions,but also build stable channels through nanopore structure to ensure the cyclic stability.This finding provides a fundamental theory for designing nanopore structures and introducing sulfur doped carbonaceous materials to enhance capacitive potassium storage and long cycle stability.展开更多
文摘Doped calcium carbonate-phosphate is a biocompatible material that influence actively on the osteogenesis, bone regenerate, strengthening of bone and dental tissues including through the skin. A mechanism of the synthesis reactions of doped nanocrystalline calcium carbonate-phosphate an oscillating type of model for these reactions is proposed. The results indicate that the synthesis involves the formation of hydroxy carbonate complexes from the three calcium carbonate polymorphs (calcite, vaterite, and aragonite) in a solution of ammonium chloride and ammonium carbonate, followed by reaction with orthophosphoric acid. The formation of nanocrystalline calcium carbonate-phosphate doped with Fe2+, Mg2+, Zn2+, K+, Si4+, and Mn2+, has been studied by X-ray diffraction, IR spectroscopy, differential thermal analysis, and energy dispersive X-ray fluorescence analysis. This ensures the preparation of a bioactive material based on octacalcium hydrogen phosphate, and calcium chloride hydroxide phosphates containing cation vacancies. Particle-size analysis data show that the materials contain nanoparticles down to 10 nm in size. Heat treatment of the doped calcium carbonate phosphates produces calcium hydroxyapatite containing cation vacancies, which can be used as a bioactive ceramic.
基金the financial support from the National Natural Science Foundation of China(No.91963118)the 111 Project(No.B13013)supported by the Open Project Program of Key Laboratory of Preparation and Application of Environmental Friendly Materials(Jilin Normal University),Ministry of Education,China(No.2020004)。
文摘Graphite as a promising anode candidate of K-ion batteries(KIBs)has been increasingly studied currently,but corresponding rate performance and cycling stability are usually inferior to amorphous carbon materials.To protect the layer structure and further boost performance,tempura-like carbon/carbon nanocomposite of graphite@pitch-derived S-doped carbon(G@PSC)is designed and prepared by a facile and low-temperature modified molten salt method.This robust encapsulation structure makes their respective advantages complementary to each other,showing mutual promotion of electrochemical performances caused by synergy effect.As a result,the G@PSC electrode is applied in KIBs,delivering impressive rate capabilities(465,408,370,332,290,and 227 m A h g^(-1)at 0.05,0.2,0.5,1,2,and 5 A g^(-1))and ultralong cyclic stability(163 m A g^(-1)remaining even after 8000 cycles at 2 A g^(-1)).On basis of ex-situ studies,the sectionalized K-storage mechanism with adsorption(pseudocapacitance caused by S doping)-intercalation(pitch-derived carbon and graphite)pattern is revealed.Moreover,the exact insights into remarkable rate performances are taken by electrochemical kinetics tests and density functional theory calculation.In a word,this study adopts a facile method to synthesize high-performance carbon/carbon nanocomposite and is of practical significance for development of carbonaceous anode in KIBs.
基金financially supported by the National Natural Science Foundation of China (Grants 21975069 and 21872045)the Key Project of Research and Development Plan of Hunan Province (Grant 2019SK2071)。
文摘Carbonaceous materials are regarded as a promising anode material for potassium ion batteries(PIBs)due to their high electronic conductivity, abundant resources and low cost. However, relatively low storage capacity and structural instability still hinder their practical application. Herein, high sulfur-doped hard carbon(SHC-3) with a sulfur up to 27.05 at% is synthesized from polystyrene and sulfur as precursors. As an anode for PIBs, the SHC-3 delivers a superb cycling stability and rate performance(298.1 mAh g^(-1)at 100 mA g^(-1) for 1000 cycles, a capacity retention of 95.2%;220.2 mAh g^(-1)at 500 mA g^(-1) after 5200 cycles). The potassium storage of SHC-3 exhibits excellent cyclic stability at both low and high rates.Structure and kinetic studies demonstrate that the larger interlayer spacing(0.382 nm) of the SHC-3 accelerates the diffusion of potassium ions and effectively alleviates the volume expansion, and thus maintains the structure stability during the process of potassization/de-potassization. Meanwhile, the density functional theory calculation shows that the doped sulfur atoms provide abundant active sites for the adsorption of potassium ions, thereby increasing the reversible capacity of PIBs. This work provides a new scheme for the design of carbonaceous anode materials with high capacity and long cycle life.
基金support of the National Natural Science Foundation of China(51971146 and 51971147)the Shanghai Municipal Science and Technology Commission(21010503100)+4 种基金the Innovation Program of Shanghai Municipal Education Commission(2019-01-07-00-07-E00015)the General Program of Natural Science Foundation of Shanghai(20ZR1438400)the Shanghai Rising-Star Program(20QA1407100)support of Shanghai Outstanding Academic Leaders Planthe Guangxi Key Laboratory of Information Materials(Guilin University of Electronic Technology,201017-K)。
文摘Integrating the merits of long lifespan and excellent energy as well as power densities,potassium-ion hybrid capacitors(PIHCs)exhibit great prospects for future energy storage devices.To boost comprehensive performance of PIHCs,heteroatom-doping and morphology-tuning as two comprehensive strategies have been devoted to designing uniquely structural carbon-based materials with favorable advantages.An ideal strategy for simultaneous atomic doping and structural regulation is expected to be developed.Herein,we propose a novel"Killing Two Birds with One Stone"strategy to prepare a tri-elements doped hollow carbon sphere(TED-HCS)as PIHCs anodes,that is,a single template of spherical CoP particles is rationally adopted,which not only provides both a P source for heteroatom-doping but also acts as a selfsacrificial template for hollow-structure engineering.The multifunctional TED-HCS presents a high capacity of 473.0 mAh g^(-1) and excellent rate performance of 212.5 mAh g^(-1) at 5.0 A g^(-1).Remarkably,the as-assembled PIHCs show outstanding energy/power density(40.4 Wh kg^(-1)/10500 W kg^(-1))and remain high-capacity retention of 89.15%even cycling 12,000 times.The"Killing Two Birds with One Stone"strategy offers new insight into the search for the preparation of carbon-based materials with multi-elements doping and specific morphology structure.
基金supported by the National Natural Science Foundation of China (No.22179123 and 21471139)the Shandong Provincial Natural Science Foundation,China (ZR2020ME038)+2 种基金the Fundamental Research Funds for the Central Universities (No.201941010)the Shandong Provincial Key R&D Plan and the Public Welfare Special Program,China (2019GGX102038)the Qingdao City Programs for Science and Technology Plan Projects (19-6-2-77-cg)。
文摘The key to construct high-energy supercapacitors is to maximize the capacitance of electrode and the voltage of the device. Realizing this purpose by utilizing sustainable and low-cost resources is still a big challenge. Herein, N, B co-doped carbon nanosheets are obtained through the proposed dual-template assisted approach by using methyl cellulose as the precursor. Due to the synergistic effects form the high surface area with the hierarchical porous structure, N/B dual doping, and a high degree of graphitization, the resultant carbon electrode exhibits a high capacitance of 572 F g^(-1)at 0.5 A g^(-1)and retains 281 F g^(-1)at 50 A g^(-1)in an acidic electrolyte. Furthermore, the symmetric device assembled using bacterial cellulose-based gel polymer electrolyte can deliver high energy density of 43 W h kg^(-1)and excellent cyclability with 97.8% capacity retention after 20 000 cycles in “water in salt” electrolyte. This work successfully realizes the fabrication of high-performance allcellulose-based quasi-solid-state supercapacitors, which brings a cost-effective insight into jointly designing electrodes and electrolytes for supporting highly efficient energy storage.
基金This study was financially supported by the National Key R&D Research Program of China(Grant No.2018YFB0905400)National Natural Science Foundationof China(Grant Nos.,51925207,U1910210,51972067,51802044,and 51872277)+2 种基金Guangdong Natural Science Funds for Distinguished Young Scholar(Grant No.2019B151502039)Fundamental Research Funds for the Central Universities of China(Grant No.WK2060140026)the DNL Cooperation Fund,CAS(Grant No.DNL180310).
文摘Solid‐state Zn–air batteries(ZABs)hold great potential for application in wearable and flexible electronics.However,further commercialization of current ZABs is still limited by the poor stability and low energy efficiency.It is,thus,crucial to develop efficient catalysts as well as optimize the solid electrolyte system to unveil potential of the ZAB technology.Due to the low cost and versatility in tailoring the structures and properties,carbon materials have been extensively used as the conductive substrates,catalytic air electrodes,and important components in the electrolytes for the solid‐state ZABs.Within this context,we discuss the challenges facing current solid‐state ZABs and summarize the strategies developed to modify properties of carbon‐based electrodes and electrolytes.We highlight the metal−organic framework/covalent organic framework‐based electrodes,heteroatom‐doped carbon,and the composites formed of carbon with metal oxides/sulfides/phosphides.We also briefly discuss the progress of graphene oxide‐based solid electrolyte.
基金supported by the projects of Sichuan Normal University(DJ GX2017017 and DJ GX2017018)
文摘Biomass-derived carbon materials have aroused widespread concern as host material of sulfur to enhance electrochemical performances for lithium–sulfur batteries. Herein, goat hair, as a low-cost and eco-friendly precursor, is employed to fabricate cauliflower-like in-situ nitrogen, oxygen and phosphorus tri-doped porous biomass carbon(NOPC) by a facile activation with H_3PO_4 and carbonization process.The morphology and microstructure of NOPC can be readily tuned by altering pyrolysis temperature. The as-prepared NOPC matrix material carbonized at 600 °C possesses 3D hierarchical porous structure, high specific surface area(535.352 m^2 g^(-1)), and appropriate pore size and pore size distribution. Encapsulating sulfur into the NOPC depends on a stem-melting technology as cathode materials of Li–S batteries. Due to the synergistic effect of special physical structure and inherent tri-doping of N, O and P, electrons and ions transfer and utilization of active sulfur in the materials are improved, and the shuttle behaviors of soluble lithium polysulfides are also mitigated. Consequently, the S/NOPC-600 composite exhibits excellent electrochemical performance, giving a high initial discharge capacity of 1185 mA h g^(-1) at 0.05 C and maintaining a relatively considerable capacity of 489 m A h g^(-1) at 0.2 C after 300 cycles. Our work shows that a promising candidate for cathode material of Li–S batteries can be synthesized using low-cost and renewable biomass materials by a facile process.
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.
文摘The use of carbon‐based materials is an appealing strategy to solve the issue of excessive CO_(2) emis‐sions.In particular,metal‐free nitrogen‐doped carbon materials(mf‐NCs)have the advantages of convenient synthesis,cost‐effectiveness,and high conductivity and are ideal electrocatalysts for the CO_(2) reduction reaction(CO_(2)RR).However,the unclear identification of the active N sites and the low intrinsic activity of mf‐NCs hinder the further development of high‐performance CO_(2)RR electrocat‐alysts.Achieving precise control over the synthesis of mf‐NC catalysts with well‐defined active N‐species sites is still challenging.To this end,we adopted a facile synthesis method to construct a set of mf‐NCs as robust catalysts for CO_(2)RR.The resulting best‐performing catalyst obtained a Far‐adaic efficiency of CO of approximately 90%at−0.55 V(vs.reversible hydrogen electrode)and good stability.The electrocatalytic performance and in situ attenuated total reflectance surface‐enhanced infrared absorption spectroscopy measurements collectively revealed that graphitic and pyridinic N can synergistically adsorb CO_(2) and H_(2)O and thus promote CO_(2) activation and protonation.
文摘The nitrogen doped graphene was synthesized by hydrothermal route utilizing 2-Chloroethylamine hydrochloride as nitrogen precursor in the presence of graphene oxide (GO). Nitrogen-doped graphene material is developed for its application in hydrogen storage at room temperature. Nitrogen doped graphene layered material shows ~1.5 wt% hydrogen storage capacity achieved at room temperature and 90 bar pressure.
文摘A variety of distinctive techniques have been developed to produce graphene sheets and their functionalized subsidiaries or composites. The production of graphene sheets by oxidative exfoliation of graphite can be a suitable route for the preparation of high volumes of graphene derivatives. P-substituted graphene material is developed for its application in hydrogen sorption in room temperature. Phosphorous doped graphene material with multi-layers of graphene shows a nearly ~2.2 wt% hydrogen sorption capacity at 298 K and 100 bar. This value is higher than that for reduced graphene oxide (RGO without phosphorous).
文摘This paper presents a new process for synthesizing a kind of nitrogen- doped carbon nanotubes (N-CNTs) with primarily a ‘graphite-like’ structure at N substitutions from flames using n-propylamine and n-butylamine as fuels. When the N-CNTs are used as the supercapacitor electrode materials, they exhibit a much larger capacitance than the regular carbon nanotubes (CNTs). It is proposed that the high proportional ‘graphite-like’ N dopant in the as-grown N-CNTs improves their surface chemical activity and conductivity and then results in a desirable performance for electro-chemical capacitors.
基金financially supported by the National Natural Science Foundation of China(22071137)。
文摘Activating MoS_(2) with atomic metal doping is promising to harvest desirable Pt-matched hydrogen evolution reaction(HER)catalytic performance.Herein,we developed an efficient method to access edgerich lattice-distorted MoS_(2) for highly efficient HER via in-situ sulphuration of atomic Co/Mo species that were well-dispersed in a formamide-derived N-doped carbonaceous(f-NC)substrate.Apart from others,pre-embedding Co/Mo species in f-NC controls the release of metal sources upon annealing in S vapor,grafting the as-made MoS_(2) with merits of short-range crystallinity,distorted lattices,rich defects,and more edges exposed.The content of atomic Co species embedded in MoS_(2) reaches up to 2.85 at.%,and its atomic dispersion has been systematically confirmed by using XRD,HRTEM,XPS,and XAS characterizations.The Co-doped MoS_(2) sample exhibits excellent HER activity,achieving overpotentials of 67 and155 m V at j=10 m A cm^(-2) in 1.0 M KOH and 0.5 M H_(2)SO_(4),respectively.Density functional theory simulations suggest that,compared with free-doping MoS_(2),the edged Co doping is responsible for the significantly improved HER activity.Our method,in addition to providing reliable Pt-matched HER catalysts,may also inspire the general synthesis of edge-rich metal-doped metal chalcogenide for a wide range of energy conversion applications.
基金financial support of grant from the Natural Science Funds for Young Scholar of China(Grant No.21107049)the priority academic program development of Jiangsu Higher Education Institution(PAPD).
文摘Hydrogen is recognized as a promising energy scours in the close future.Online hydrogen preparation from formic acid under mild reaction conditions causes extensive interests.Mo_(2)C and metal(Fe,Ni,Co,K)doped Mo_(2)C on granular activated carbon(GAC)were prepared and used as heterogeneous catalysts for H2 generation from formic acid on a fixed bed reactor at 100–250°C.The formic acid conversions on doped Mo_(2)C-Me/GAC are clearly improved,especially at lower reaction temperatures.Co doping presents outstanding effect on H2 selectivity and conversion rate compared to Ni and Fe.A 56.3%formic acid conversion was reached on Mo_(2)C-Co/GAC at 100°C,which triples that on Mo_(2)C/GAC at the same temperature.At 150°C,a high formic acid conversion over 90%was reached on Mo_(2)C-Co/GAC.These long lifetime catalysts with no precious metal provide a low cost route to hydrogen production from formic acid.
基金supported by the National Natural Science Foundation of China (Grant Nos.51872236,52072307)MOE SUTD Kickstarter Innitiative (SKI 2021_02_16).
文摘The unique structural features of hard carbon(HC)make it a promising anode candidate for sodium-ion batteries(SIB).However,traditional methods of preparing HC require special equipment,long reaction times,and large energy consumption,resulting in low throughputs and efficiency.In our contribution,a novel synthesis method is proposed,involving the formation of HC nanosheets(NS-CNs)within minutes by creating an anoxic environment through flame combustion and further introducing sulfur and nitrogen sources to achieve heteroatom doping.The effect of heterogeneous element doping on the microstructure of HC is quantitatively analyzed by high-resolution transmission electron microscopy and image processing technology.Combined with density functional theory calculation,it is verified that the functionalized HC exhibits stronger Na^(+)adsorption ability,electron gain ability,and Na^(+) migration ability.As a result,NS-CNs as SIB anodes provide an ultrahigh reversible capacity of 542.7mAh g^(-1) at 0.1Ag^(-1),and excellent rate performance with a reversible capacity of 236.4mAh g^(-1) at 2Ag^(-1) after 1200 cycles.Furthermore,full cell assembled with NS-CNs as the can present 230mAh g^(-1) at 0.5Ag^(-1) after 150 cycles.Finally,in/ex situ techniques confirm that the excellent sodium storage properties of NS-CNs are due to the construction of abundant active sites based on the novel synthesis method for realizing the reversible adsorption of Na^(+).This work provides a novel strategy to develop novel carbons and gives deep insights for the further investigation of facile preparation methods to develop high-performance carbon anodes for alkali-ion batteries.
基金supported by the National Natural Science Foundation of China(No. 51802122)the Natural Science Fund of Hubei Province(No.2017CFB155)+4 种基金China Scholarship Council (No. 201808420401)Scientific Research Plan Project of Hubei Education Department(No. B2017269)Scientific Research Initial funding for the Advanced Talent of Jianghan University (No. 1009-06810001)Opening Project of Key Laboratory of Optoelectronic Chemical Materials and Devices, Ministry of Education, Jianghan University(Nos. JDGD-201702,JDGD-201811)Hubei Provincial Department of Education for the "Chutian Scholar" program
文摘In this work, nitrogen doped clews-like carbon materials were successfully fabricated through hydrothermal polymerization method, followed by post treatment that integrated the carbonization,activation and post-nitrogen doping into one process. This preparation method can form particular hierarchical porous structure without using any sacrificial templates. The experimental results show that the nitrogen doped clews-like hierarchical porous carbon materials possess a relatively high specific surface area of 815 m^2/g with the nitrogen content of 10.58 at%. The electrochemical properties show that the resulting sample delivers 258 F/g at a 0.5 A/g and excellent capacity retention of 79% at 20 A/g. After conducting 10,000 charge-discharge cycles at 10 A/g, the capacitance retention of 98.3% is achieved.These intriguing results demonstrate that the obtained nitrogen doped clews-like carbon materials will be promising electrode materials for supercapacitor and other energy storage devices.
基金funding support from the Ministry of Science and Technology of China (No. 2012CB933403)Beijing Natural Science Foundation (No. 2182086)the National Natural Science Foundation of China (Nos. 51425302, 51302045)。
文摘In recent years, especially when there is increasing concern about the safety issue of lithium-ion batteries (LIBs), aqueous Zn-ion batteries (ZIBs) have been getting a lot of attention because of their cost-effectiveness, materials abundance, high safety, and ecological friendliness. Their working voltage and specific capacity are mainly determined by their cathode materials. Vanadium oxides are promising cathode materials for aqueous ZIBs owing to their low cost, abundant resources, and multivalence. However, vanadium oxide cathodes still suffer from unsatisfactory capacity, poor stability, and low electrical conductivity. In this work, cascading V_(2)O_(3)/nitrogen doped carbon (V_(2)O_(3)/NC) hybrid nanosheets are prepared for high-performance aqueous ZIBs by pyrolyzing pentyl viologen dibromide (PV) intercalated V_(2)O5 nanosheets. The unique structure features of V_(2)O_(3)/NC nanosheets, including thin sheet-like morphology, small crystalline V_(2)O_(3) nanoparticles, and conductive NC layers, endow V_(2)O_(3)/NC with superior performance compared to most of the reported vanadium oxide cathode materials for aqueous ZIBs. The V_(2)O_(3)/NC cathode exhibits the discharge capacity of 405 mAh/g at 0.5 A/g, excellent rate capability (159 mAh/g at 20 A/g), and outstanding cycling stability with 90% capacity retention over 4000 cycles at 20 A/g.
基金financial support from the NSFC(Nos.51361005,U1501242,51371060 and 51671062)the Guangxi Natural Science Foundation(Nos.AD17195073,2014GXNSFAA118319 and 2014GXNAFDA118005)+1 种基金the Guangxi Key Laboratory of Information Materials(Nos.161002-Z and 161002-K)the Guangxi Scientific Technology Team(No.2012GXNSFGA06002)
文摘Nitrogen-doped porous carbon materials(NPCs) have been successfully fabricated by a simple one-step pyrolysis of diethylenetriaminepentaacetic acid(DTPA) in the presence of KOH. The as-synthesized NPCs displayed a high specific surface area(3214 m;g;) and a well-defined porous structure when the annealing temperature reached 800 ℃, which showed superior electrochemical performance as supercapacitor electrode materials. Electrochemical tests showed that the NPCs achieved an impressive specific capacitance of 323 F g;at a current density of 0.5 A g;in 6 M KOH aqueous solution and an outstanding cycle stability, negligible specific capacitance decay after 5000 cycles at 10 A g;. This strategy offered a new insight into the preparation of novel carbon materials for the advanced energy storage devices, such as supercapacitors, fuel cells and lithium ion batteries.
基金the Youth Talent Program Startup Foundation of Qufu Normal University(No.602601)the Natural Science Foundation of Rizhao(No.RZ2021ZR37)。
文摘Due to their superior fluorescence,phosphorescence,and catalytic capabilities,carbon dots(CDs),an emerging class of fluorescent carbon nanomaterials,have a wide range of potential applications.The properties of CDs have recently been controlled extensively by heteroatom doping.Boron atoms have been effectively doped into the structure of CDs due to their similar size to carbon atoms and excellent electron-absorbing ability to further improve the performance of CDs.In this review,we summarize the research progress of boron-doped CDs in recent years from the aspects of doping strategies,effects of boron doping on different performances of CDs and applications.Starting from the two aspects of single boron doping and boron and other atom co-doping,from different precursor materials to different synthesis methods,the doping strategies of boron-doped CDs are reviewed in detail.Then,the effects of boron doping on the fluorescence,phosphorescence and catalytic performance of CDs and applications of boron-doped CDs in optical sensors,information encryption and anti-counterfeiting are discussed.Finally,we further provide a prospect towards the future development of boron-doped CDs.
基金supported by the Key R&D Plan of Jihua Laboratory(Nos.X200191TL200 and X220301XS220)Guangdong Basic and Applied Basic Research Foundation(No.2022A1515110052)+1 种基金Foshan Postdoctoral Science Foundation(Nos.X221071MS210)Numerical computations were performed on Hefei advanced computing center。
文摘Sulfur doped carbonaceous materials are promising anodes for potassium-ion batteries because of their ability to bridge active sites and induce C/S electron coupling,resulting in increased ion storage capacitance However,the large potassium ions could cause significant volume expansion and structure collapse during operation in sulfur doped carbonaceous anodes,which lead to rapidly capacity sacrifice during long-term cycling.Nanopore design for anchoring sulfur atom in carbon skeleton is a novel way to alleviate the structure collapse and maintain the cycling stability.Therefore,this study developed a controlled nanopore and sulfur doped carbon sphere structure(S-NPHCSs).In potassium-ion batteries S-NPHCSs anode demonstrated exceptional performance with a high reversible capacity of 247 mAh·g^(–1)after 50 cycles at 0.2 A·g^(–1)and delivered a long cycle stability of 600 cycles at a high current density of 1.0 A·g^(–1).Interconnected nanopores and doped sulfur structure not only expand the accumulation space and offer ample active sites for diffusion and adsorption of potassium ions,but also build stable channels through nanopore structure to ensure the cyclic stability.This finding provides a fundamental theory for designing nanopore structures and introducing sulfur doped carbonaceous materials to enhance capacitive potassium storage and long cycle stability.