Two-dimensional transition metal dichalcogenides(TMDs)show great promise for developing the next generation of electronic and optoelectronic devices.However,most TMDs have n-type or n-dominant bipolar characteristics,...Two-dimensional transition metal dichalcogenides(TMDs)show great promise for developing the next generation of electronic and optoelectronic devices.However,most TMDs have n-type or n-dominant bipolar characteristics,and this severely limits their potential for being designed as multi-functional heterostructures.Recently,thermal annealing has been reported as an easy means of p-doping TMDs,but the mechanism remains ambiguous,thereby preventing reliable outcomes and it becoming a mature doping technology for TMDs.Here,the mechanism of thermal annealing for p-doping a 2D selenide is investigated thoroughly,revealing the key role of the catalytic effect of nano-thick gold electrodes in achieving p-doping.As an example,2D SnSe_(2)with a fairly high electron density of∼10^(18)cm^(−3)is used,and its electrical performance is greatly enhanced after thermal annealing when 30-nm-thick gold electrodes are deposited.The results of performing XPS and Auger electron spectroscopy on samples before and after annealing show that the p-doping effect is due to the oxidation of selenide atoms,during which the gold acts as a critical catalytic element.This method is also shown to be valid for other 2D selenides including WSe_(2)and MoSe_(2),and the present findings offer new avenues for enriching the electrical properties of 2D selenides by means of annealing.展开更多
The fabrication of efficient and stable catalysts to accelerate the kinetics of the hydrogen evolution reaction(HER)is a crucial step in the development of sustainable energy production.The structural design of Pt-bas...The fabrication of efficient and stable catalysts to accelerate the kinetics of the hydrogen evolution reaction(HER)is a crucial step in the development of sustainable energy production.The structural design of Pt-based catalysts with efficient atom utilization remains a pivotal factor in the continued advancement of HER catalysts.In this work,we synthesized phosphorylated Mo-based particles embedded in P-doped carbon materials for the optimized loading of platinum nanoparticles(Pt/Mo-P@C).Theoretical results indicate that the catalytic efficacy of the materials can be enhanced by altering the electronic structure of Pt nanoparticles through the precise formation of Pt-Mo bond and multiple heterostructures.The catalysts exhibited exceptional mass activity after low-temperature reduction,achieving a current density of 100 mA·cm−2 at 54.4 mV,which is lower than that of the commercial Pt/C catalyst.Furthermore,the mass activity of the main catalyst was 6.7 times greater than that of the commercial Pt/C catalyst at an overpotential of 50 mV.展开更多
The industrial implementation of Solar-driven photocatalysis is hampered by inefficient charge separation,poor reusability and hard retrieval of powdery catalysts.To conquer these drawbacks,a self-floating S-scheme Bi...The industrial implementation of Solar-driven photocatalysis is hampered by inefficient charge separation,poor reusability and hard retrieval of powdery catalysts.To conquer these drawbacks,a self-floating S-scheme Bi_(4)O_(5)Br_(2)/P-doped C_(3)N_(4)/carbon fiber cloth(BB/PN/CC)composed of carbon fibers(CC)as the core and Bi_(4)O_(5)Br_(2)/P-doped C_(3)N_(4)(BB/PN)nanosheets as the shell was constructed as a competent,recyclable cloth-shaped photocatalyst for safe and efficient degradation of aquacultural antibiotics.The BB/PN/CC fabric achieves an exceptional tetracycline degradation rate constant of 0.0118 min‒1,surpassing CN/CC(0.0015 min^(‒1)),BB/CC(0.0066 min^(‒1))and PN/CC(0.0023 min^(‒1))by 6.9,0.8 and 4.1 folds,respectively.Beyond its catalytic prowess,the photocatalyst’s practical superiority is evident in its effortless recovery and environmental adaptability.The superior catalytic effectiveness stems from the S-scheme configuration,which retains the maximum redox capacities of the constituent BB and PN while enabling efficient spatial detachment of photo-carriers.X-ray photoelectron spectroscopy(XPS),in-situ XPS,and electron paramagnetic resonance analyses corroborate the S-scheme mechanism,revealing electron accumulation on PN and hole retention on BB under illumination.Density functional theory calculations further confirm S-scheme interfacial charge redistribution and internal electric field formation.This study advances the design of macroscopic S-scheme heterojunction photocatalysts for sustainable water purification.展开更多
Exclusive responsiveness to ultraviolet light (~3.2 eV) and high photogenerated charge recombination rate are the two primary drawbacks of pure TiO_(2). We combined N-doped graphene quantum dots (N-GQDs), morphology r...Exclusive responsiveness to ultraviolet light (~3.2 eV) and high photogenerated charge recombination rate are the two primary drawbacks of pure TiO_(2). We combined N-doped graphene quantum dots (N-GQDs), morphology regulation, and heterojunction construction strategies to synthesize N-GQD/N-doped TiO_(2)/P-doped porous hollow g-C_(3)N_(4) nanotube (PCN) composite photocatalysts (denoted as G-TPCN). The optimal sample (G-TPCN doped with 0.1wt% N-GQD, denoted as 0.1% G-TPCN) exhibits significantly enhanced photoabsorption, which is attributed to the change in bandgap caused by elemental doping (P and N), the improved light-harvesting resulting from the tube structure, and the upconversion effect of N-GQDs. In addition, the internal charge separation and transfer capability of0.1% G-TPCN are dramatically boosted, and its carrier concentration is 3.7, 2.3, and 1.9 times that of N-TiO_(2), PCN, and N-TiO_(2)/PCN(TPCN-1), respectively. This phenomenon is attributed to the formation of Z-scheme heterojunction between N-TiO_(2) and PCNs, the excellent electron conduction ability of N-GQDs, and the short transfer distance caused by the porous nanotube structure. Compared with those of N-TiO_(2), PCNs, and TPCN-1, the H2 production activity of 0.1%G-TPCN under visible light is enhanced by 12.4, 2.3, and 1.4times, respectively, and its ciprofloxacin (CIP) degradation rate is increased by 7.9, 5.7, and 2.9 times, respectively. The optimized performance benefits from excellent photoresponsiveness and improved carrier separation and migration efficiencies. Finally, the photocatalytic mechanism of 0.1% G-TPCN and five possible degradation pathways of CIP are proposed. This study clarifies the mechanism of multiple modification strategies to synergistically improve the photocatalytic performance of 0.1% G-TPCN and provides a potential strategy for rationally designing novel photocatalysts for environmental remediation and solar energy conversion.展开更多
Catalysts for oxygen conversion play an important role in energy storage and conversion technologies such as metal-air batteries.Developing highly active stable,and low-cost catalysts is critical for further implement...Catalysts for oxygen conversion play an important role in energy storage and conversion technologies such as metal-air batteries.Developing highly active stable,and low-cost catalysts is critical for further implementation of the above technologies.Herein,an efficien oxygen electrocatalyst with Co_(2)P nanoparticles(NPs)coupling onto N,P-doped porous carbon nanosheets(Co_(2)P@NPAC)derived from cotton stalk is successfully designed and prepared via activation,hydrothermal treatment,and pyrolysis procedure.The excellent properties of electrical conductivity,mass transfer,and synergistic integration between Co_(2)P and N,P-doped carbon endow Co_(2)P@NPAC composite with superior oxygen reduction reaction/oxygen evolution reaction(ORR/OER)performance.Co_(2)P@NPAC catalyst achieves ORR activity with half-wave potential of 0.85 V and high OER activity with overpotential of 261 mV at 10 mA·cm^(-2).The flexible Zn-air batteries(ZABs)based on Co_(2)P@NPAC catalyst revea outstanding performances with a high open-circuit voltage(1.38 V),a peak power density of(75 mW·cm^(-2)),and a low charge-discharge voltage gap(0.74 V,~200 cycles)The flexible ZABs express the stable discharge-charge voltage gap at various bending states.This work provides interesting inspiration for the ingenious design of efficien carbon electrocatalysts from biomass with potential application of energy storage and conversion devices.展开更多
It is necessary to adopt a specific strategy to construct an efficient and low-cost transition metal-based composite to replace the precious metal-based electrocatalyst for OER catalytic processes.In this work,a beade...It is necessary to adopt a specific strategy to construct an efficient and low-cost transition metal-based composite to replace the precious metal-based electrocatalyst for OER catalytic processes.In this work,a beaded stream-like N and P-codoped carbon-coated Fe_(3)O_(4)nanocomposite(N,P-Fe_(3)O_(4)@C)is derived from MIL-88A by two-step annealing.The unique 3D nanostructure and amorphous N-doped carbon layer enlarge the number of active sites,and P doping changes the pathway from AEM to LOM.The synergistic effect of these factors results in N,P-Fe_(3)O_(4)@C presenting excellent OER catalytic activity with an overpotential of 201 mV(η10),a Tafel slope of 57.1 mV/dec and stable operation for 100 h(the current density is 10 mA/cm^(2)).Density functional theory calculations and electrochemical tests reveal that the P doping enhances the overlap of Fe 3d orbital bands and O 2p orbitals,and thus significantly increases the metaloxygen covalency,triggering the pathway transition from AEM to LOM.This work provides a new way to construct more efficient transition metal-based composite carbon materials.展开更多
Hydrogen production by photolysis of water by sunlight is an environmentally-friendly preparation technology for renewable energy.Graphitic carbon nitride(g-C3N4),despite with obvious catalytic effect,is still unsatis...Hydrogen production by photolysis of water by sunlight is an environmentally-friendly preparation technology for renewable energy.Graphitic carbon nitride(g-C3N4),despite with obvious catalytic effect,is still unsatisfactory for hydrogen production.In this work,phosphorus element is incorporated to tune g-C3N4's property through calcinating the mixture of g-C3N4 and Na H2PO2,sacrificial agent and co-catalyst also been supplied to help efficient photocatalytic hydrogen production.Phosphorus(P)doped g-C3N4 samples(PCN-S)were prepared,and their catalytic properties were studied.X-ray diffraction(XRD),X-ray photoelectron spectroscopy(XPS),scanning electron microscopy(SEM)and ultraviolet diffuse reflection(UV-DRS)were used to study their structures and morphologies.The results show that the reaction rate of PCN-S is 318μmol·h^-1·g^-1,which is 2.98 times as high as pure carbon nitride nanosheets(CN)can do.Our study paves a new avenue,which is simple,environment-friendly and sustainable,to synthesize highly efficient P doping g-C3N4 nanosheets for solar energy conversion.展开更多
Chemically modified carbonaceous materials have attained utmost attention in the fields of renewable energy storage and conversion,due to the controllable physicochemical properties,tailorable micro-/nanostructures,an...Chemically modified carbonaceous materials have attained utmost attention in the fields of renewable energy storage and conversion,due to the controllable physicochemical properties,tailorable micro-/nanostructures,and respectable stability.Herein,P-doped mesoporous carbons were synthesized by using F127 as the soft template,organophosphonic acid as the P source and phenolic resin as the carbon source.Small amounts of iron species were introduced to act as a graphitization catalyst.The synthesized carbons exhibit the well-defined wormhole-like pore structure featuring high specific surface area and homogenously doped P heteroatoms.Notably,introducing iron species during the synthesis process can optimize the textural properties and the degree of graphitization of carbon materials.The doping amount of P has an important effect on the porous structure and the defect degree,which correspondingly influence the active sites and the oxygen reduction reaction(ORR)activity.The resultant material presents superior catalytic activity for the ORR,together with remarkably enhanced durability and methanol tolerance in comparison with the commercial Platinum catalyst,demonstrating the possibility for its use in electrode materials and electronic nanodevices for metal-air batteries and fuel cells.展开更多
We report for the first time a Na-ion battery anode material composed of P-doped CoSe_(2)nanoparticles(P-CoSe_(2))with the size of 5–20 nm that are uniformly embed in a 3 D porous honeycomb-like carbon network.High r...We report for the first time a Na-ion battery anode material composed of P-doped CoSe_(2)nanoparticles(P-CoSe_(2))with the size of 5–20 nm that are uniformly embed in a 3 D porous honeycomb-like carbon network.High rate capability and cycling stability are achieved simultaneously.The honeycomb-like carbon network is rationally designed to support high electrical conductivity,rapid Na-ion diffusion as well as the accommodation of the volume expansion from the active P-CoSe_(2)nanoparticles.In particular,heteroatom P-doping within CoSe_(2)introduces stronger P-Co bonds and additional P-Se bonds that significantly improve the structure stability of P-CoSe_(2)for highly stable sodiation/desodiation over long-term cycling.P-doping also improves the electrical conductivity of the CoSe_(2)nanoparticles,leading to highly elevated electrochemical kinetics to deliver high specific capacities at high current densities.Benefiting from the unique nanostructure and atomic-level P-doping,the P-CoSe_(2)(2:1)/C anode delivers an excellent cycle stability with a specific capacity of 206.9 mA h g^(-1)achieved at 2000 mA g^(-1)after 1000 cycles.In addition,this material can be synthesized using a facile pyrolysis and selenization/phosphorization approach.This study provides new opportunities of heteroatom doping as an effective method to improve the cycling stability of Na-ion anode materials.展开更多
Graphite carbon nitride(g-C_(3)N_(4)) is a promising non-metal photocatalyst for photocatalytic hydrogen production, but its performance is still limited due to sluggish charges separation and low utilization of light...Graphite carbon nitride(g-C_(3)N_(4)) is a promising non-metal photocatalyst for photocatalytic hydrogen production, but its performance is still limited due to sluggish charges separation and low utilization of light.In this work, P-doped and N-doped carbon dots(NCDs) supported g-C_(3)N_(4)were successfully prepared via hydrothermal and polymerization reactions. The sub-bandgap formed by P-doping enhances the utilization of visible light, and the high electron density of P sites is conducive to the trapping of holes. NCDs also improve light utilization and, more importantly, act as electron acceptors and transporters to promote electron transport. The built-in electric field formed by the synergy of P-doping and NCDs-loading greatly promotes the separation of charges. The PCN/NCDs showed a significantly improved hydrogen evolution activity of 3731 μmol h^(-1)g^(-1), which was 6.7 times that of pure carbon nitride(560 μmol h^(-1)g^(-1)). This strategy may be generalized to the design of g-C_(3)N_(4)-based photocatalysts, facilitating the separation of charges for enhanced catalytic activity.展开更多
Four kinds of polythiophenes have been doped with CH3SO3H in CHCl3 under air,oxygen,and nitrogen. In the doping of two types of poly(3-hexylthiophene)s,P3HexTh(Zn/Ni)and P3HexTh(Fe)with different contents of a head-to...Four kinds of polythiophenes have been doped with CH3SO3H in CHCl3 under air,oxygen,and nitrogen. In the doping of two types of poly(3-hexylthiophene)s,P3HexTh(Zn/Ni)and P3HexTh(Fe)with different contents of a head-to-tail unit,the p-doping occurs at a similar rate.The reaction between poly(3-dodecylthiophene),P3DodTh,and the acid takes place more rapidly.P3OBuTh with a butoxy substituent undergoes more facile p-doping and receives photochemical reaction with CHCl3,and this reaction obeys a pseudo-first-order rate law with a rate constant kobs of 1.42×10-5s-1at room tempera- ture.展开更多
Owing to the advantages of high energy density,low cost,abundant sulfur reserves and environmentally friendly nature,lithium-sulfur batteries(LSBs)were considered as one of the potential candidates of energy storage d...Owing to the advantages of high energy density,low cost,abundant sulfur reserves and environmentally friendly nature,lithium-sulfur batteries(LSBs)were considered as one of the potential candidates of energy storage devices for the next generation.However,the significant challenges in this area stem from the sluggish reaction kinetics of the insoluble Li_(2)S product and the capacity degradation triggered by the severe shuttle effect of polysulfides.It has been firmly established through numerous studies that modifying separators is an effective approach to enhance the properties of LSBs by facilitating the catalytic kinetic conversion and chemical adsorption of lithium polysulfides(Li PSs).In this work,we report a straightforward method for fabrication of the phosphorus doped porous CeO_(2)(P-CeO_(2))as separator modifier to accelerate the catalytic kinetic conversion of polysulfides and effectively inhibit the shuttle effect in LSBs.Through coin batteries tests,P-CeO_(2)modified PP separator(P-CeO_(2)//PP)exhibits remarkable electrochemical performance.It demonstrates a high initial capacity of 1180 mAh/g at 0.5 C,surpassing the performance of the bare CeO_(2)//PP separator.Furthermore,the P-CeO_(2)//PP separator demonstrates enhanced cycling stability,with a low-capacity fading rate of only 0.048%per cycle over 1000 cycles at 2 C.In compared with bare CeO_(2)//PP,P-CeO_(2)//PP exhibits high redox peak current,enhanced adsorption property of Li_(2)S_(6)and early Li_(2)S precipitation.These results highlight the superior performance of the P-CeO_(2)//PP separator compared to the bare CeO_(2)//PP separator.Hence,this research presents a successful strategy for the modification of LIBs separator with improved electrochemical performance and cycle stability.展开更多
The biomass electrochemical oxidation coupled with hydrogen evolution reaction has received widespread attention due to its carbon-neutral and sustainable properties.The electrosynthesis of 2,5-furanodicarboxylic acid...The biomass electrochemical oxidation coupled with hydrogen evolution reaction has received widespread attention due to its carbon-neutral and sustainable properties.The electrosynthesis of 2,5-furanodicarboxylic acid(FDCA)from 5-hydroxymethylfurfural(HMF)oxidation is one of the most promising means for the production of bioplastic monomers.In this work,we constructed a novel P-doped Ni_(3)S_(2)and Ni heterojunction on nickel foam(P-Ni_(3)S_(2)/Ni/NF)using electrodeposition methods and thermal sulfuration techniques as a bifunctional catalyst for the simultaneous anodic oxidation of HMF to FDCA(HMFOR)and the cathodic hydrogen evolution reaction(HER).On one hand,the synergistic promotion of P doping and the heterojunction of Ni_(3)S_(2)and Ni accelerated electron transfer,and on the other hand,the structure of three-dimensional microsphere stacking on NF surface to form macropores enhances the exposure of catalytically active sites.The prepared P-Ni_(3)S_(2)/Ni/NF exhibited remarkable performance with high HMF conversion(99.2%),FDCA yield(98.1%),and Faraday efficiency(98.8%),and excellent stability with good product selectivity for 7 consecutive cycles,which stands at a higher level than majority of previously published electrocatalysts.Furthermore,P-Ni_(3)S_(2)/Ni/NF also shows a significant response in HER.By using HMFOR and HER as the anodic reaction and cathodic reaction,respectively,the biomass upgrading and hydrogen production can be carried out simultaneously.The synthesized P-Ni_(3)S_(2)/Ni/NF only need a voltage of 1.31V to achieve a current density of 10mA/cm^(2)in a two-electrode system of HMFOR and HER,which is much lower than that of 1.48 V in OER and HER process,thus potentially reducing the cost of this process.展开更多
Lithium–sulfur(Li–S)batteries have attracted much attention due to their ultrahigh theoretical specific capacity.However,serious capacity attenuation caused by shuttle effect still inhibits the performance improveme...Lithium–sulfur(Li–S)batteries have attracted much attention due to their ultrahigh theoretical specific capacity.However,serious capacity attenuation caused by shuttle effect still inhibits the performance improvement.Herein,a modified separator consists of the few-layer graphene as a highly conductive network and stable scaffold to support P-doped boron nitride(denoted as BN-P@GO)as the functional interlayer of Li–S batteries.The cell with the interlayer provides an initial discharge capacity as high as1045.3 mAh g^-1,and retains a high reversible capacity of 728.7 mAh g^-1 at 1 C after 500 cycles with a capacity decay of 0.061%per cycle.Moreover,the rate capability is also superior to cells with BN@GO or BN-P interlayers,i.e.reversible capcity of 457.9 mAh g^-1 even at 3 C.The excellent electrochemical performance is ascribed to the synergistic effect of physical barrier and chemical adsorption for dissolved polysulfides provided by the modified layer.Furhtermore,it also mitigates the polarization and promotes kinetic reactions of the cells.This work provides a concise and effective method for commercialization of lithium–sulfur batteries.展开更多
g-C3N4 is a metal-free semiconductor and a potential candidate for photocatalytic H2 production,however,the drawbacks,rapid recombination rate and limited migration efficiency of photogenerated carriers,restrict its p...g-C3N4 is a metal-free semiconductor and a potential candidate for photocatalytic H2 production,however,the drawbacks,rapid recombination rate and limited migration efficiency of photogenerated carriers,restrict its photocatalytic activity.Herein,Co(II)as a hole cocatalyst modified P-doped g-C3N4 were successfully prepared to ameliorate the separation efficiency of photoinduced carriers and enhance the photocatalytic hydrogen production.The photocatalytic results demonstrated that the P-doped g-C3N4(PCN)exhibited higher photocatalytic activity compared with pure g-C3N4,while Co(II)/PCN photocatalyst exhibited further enhancement of photocatalytic performance.The proposed possible mechanism based on various characterizations is that P-doping can modulate the electronic structure of g-C3N4 to boost the separation of photogenerated-e-and h+;while the synergistic effect of both Co(II)(as hole cocatalyst)and Pt(as electron cocatalyst)can not only lead to the directional shunting of photogenerated e+-h?pairs,but further accelerate the photogenerated electrons transfer to Pt in order to join the photocatalytic reduction process for hydrogen evolution.As a result,the transportation and separation of photoinduced carriers were accelerated to greatest extent in the Pt/Co(II)/PCN photocatalyst.展开更多
Self-assembled nanostructure arrays integrating the advantages of the intrinsic characters of nanostructure as well as the array stability are appealing in advanced materials.However,the precise bottom-up synthesis of...Self-assembled nanostructure arrays integrating the advantages of the intrinsic characters of nanostructure as well as the array stability are appealing in advanced materials.However,the precise bottom-up synthesis of nanostructure arrays without templates or substrates is quite challenging because of the general occurrence of homogeneous nucleation and the difficult manipulation of noncovalent interactions.Herein,we first report the precisely manipulated synthesis of well-defined louver-like P-doped carbon nitride nanowire arrays(L-PCN)via a supramolecular self-assembly method by regulating the noncovalent interactions through hydrogen bond.With this strategy,CN nanowires align in the outer frame with the separation and spatial location achieving ultrastability and outstanding photoelectricity properties.Significantly,this self-assembly L-PCN exhibits a superior visible light-driven hydrogen evolution activity of 1872.9μmol h^−1 g^−1,rendering a^25.6-fold enhancement compared to bulk CN,and high photostability.Moreover,an apparent quantum efficiency of 6.93%is achieved for hydrogen evolution at 420±15 nm.The experimental results and first-principles calculations demonstrate that the remarkable enhancement of photocatalytic activity of L-PCN can be attributed to the synergetic effect of structural topology and dopant.These findings suggest that we are able to design particular hierarchical nanostructures with desirable performance using hydrogen-bond engineering.展开更多
Structural design and elemental doping are research hotspots for the preparation of lightweight absorbers with high absorption performance and low filling ratio.Herein,a P-doped hydrangea-like layered compos-ite(Co_(2...Structural design and elemental doping are research hotspots for the preparation of lightweight absorbers with high absorption performance and low filling ratio.Herein,a P-doped hydrangea-like layered compos-ite(Co_(2)P/Ni_(2)P@C)encapsulated with Ni-LDH was successfully synthesized by solvothermal method fol-lowed by phosphorization.The defects generated by P doping and the generation of multilayered nonuni-form interfaces enhance the dielectric loss induced by polarization.Simultaneously,the magnetic phos-phides induce magnetic loss and modulate the dielectric properties of the carbon matrix to enhance the conductive loss.The multilayered hollow structure of this composite promotes the scattering and reflec-tion of electromagnetic waves and optimizes the impedance characteristics.As a result,the multilayered hollow Co_(2)P/Ni_(2)P@C composite exhibits an optimum reflection loss value(RL)of–64.6 dB at 15.1 GHz with a thickness of 2 mm and a filler ratio of only 10 wt%.The radar cross-section(RCS)attenuation further demonstrates that the material can dissipate microwave energy in practical applications.Overall,this work provides an effective development strategy for the design of multilayered high-performance electromagnetic wave(EMW)absorbers doped with strongly polarized elements.展开更多
Optimizing the intrinsic activity of non-noble metal by precisely tailoring electronic structure offers an appealing way to construct cost-effective catalysts for selective biomass valorization.Herein,we reported a P-...Optimizing the intrinsic activity of non-noble metal by precisely tailoring electronic structure offers an appealing way to construct cost-effective catalysts for selective biomass valorization.Herein,we reported a P-doping bifunctional catalyst(Ni-P/mSiO_(2))that achieved 96.6%yield for the hydrogenation rearrangement of furfural to cyclopentanone at mild conditions(1 MPaH_(2),150°C).The turnover frequency of Ni-P/mSiO_(2)was 411.9 h^(-1),which was 3.2-fold than that of Ni/mSiO_(2)(127.2 h^(-1)).Detailed characterizations and differential charge density calculations revealed that the electron-deficient Niδ+species were generated by the electron transfer from Ni to P,which promoted the ring rearrangement reaction.Density functional theory calculations illustrated that the presence of P atoms endowed furfural tilted adsorb on the Ni surface by the C=O group and facilitated the desorption of cyclopentanone.This work unraveled the connection between the localized electronic structures and the catalytic properties,so as to provide a promising reference for designing advanced catalysts for biomass valorization.展开更多
Photosensors with versatile functionalities have emerged as a cornerstone for breakthroughs in the future optoelectronic systems across a wide range of applications.In particular,emerging photoelectrochemical(PEC)-typ...Photosensors with versatile functionalities have emerged as a cornerstone for breakthroughs in the future optoelectronic systems across a wide range of applications.In particular,emerging photoelectrochemical(PEC)-type devices have recently attracted extensive interest in liquid-based biosensing applications due to their natural electrolyte-assisted operating characteristics.Herein,a PEC-type photosensor was carefully designed and constructed by employing gallium nitride(GaN)p-n homojunction semiconductor nanowires on silicon,with the p-GaN segment strategically doped and then decorated with cobalt-nickel oxide(CoNiO_(x)).Essentially,the p-n homojunction configuration with facile p-doping engineering improves carrier separation efficiency and facilitates carrier transfer to the nanowire surface,while CoNiO_(x)decoration further boosts PEC reaction activity and carrier dynamics at the nanowire/electrolyte interface.Consequently,the constructed photosensor achieves a high responsivity of 247.8 mA W^(-1)while simultaneously exhibiting excellent operating stability.Strikingly,based on the remarkable stability and high responsivity of the device,a glucose sensing system was established with a demonstration of glucose level determination in real human serum.This work offers a feasible and universal approach in the pursuit of high-performance bio-related sensing applications via a rational design of PEC devices in the form of nanostructured architecture with strategic doping engineering.展开更多
The electronic structure of catalytic active sites can be influenced by modulating the coordination bonding of the central single metal atom,but it is difficult to achieve.Herein,we reported the single Zn-atom incorpo...The electronic structure of catalytic active sites can be influenced by modulating the coordination bonding of the central single metal atom,but it is difficult to achieve.Herein,we reported the single Zn-atom incorporated dual doped P,N carbon framework(Zn-N_(4)P/C)for ORR via engineering the surrounding coordination environment of active centers.The Zn-N_(4)P/C catalyst exhibited comparable ORR activity(E_(1/2)=0.86 V)and significantly better ORR stability than that of Pt/C catalyst.It also shows respectable performance in terms of maximum peak power density(249.6 mW cm^(-2)),specific capacitance(779 mAh g^(-1)),and charge-discharge cycling stability for 150 hours in Zn-air battery.The high catalytic activity is attributed to the uniform active sites,tunable electronic/geometric configuration,optimized intrinsic activity,and faster mass transfer during ORR-pathway.Further,theoretical results exposed that the Zn-N_(4)P configuration is more electrochemically active as compared to Zn-N_(4) structure for the oxygen reduction reaction.展开更多
基金supported by the National Natural Science Foundation of China(Grant Nos.52075385 and 12034001)the National Key R&D Program(Grant No.2018YFA0307200)the 111 Project(Grant No.B07014).
文摘Two-dimensional transition metal dichalcogenides(TMDs)show great promise for developing the next generation of electronic and optoelectronic devices.However,most TMDs have n-type or n-dominant bipolar characteristics,and this severely limits their potential for being designed as multi-functional heterostructures.Recently,thermal annealing has been reported as an easy means of p-doping TMDs,but the mechanism remains ambiguous,thereby preventing reliable outcomes and it becoming a mature doping technology for TMDs.Here,the mechanism of thermal annealing for p-doping a 2D selenide is investigated thoroughly,revealing the key role of the catalytic effect of nano-thick gold electrodes in achieving p-doping.As an example,2D SnSe_(2)with a fairly high electron density of∼10^(18)cm^(−3)is used,and its electrical performance is greatly enhanced after thermal annealing when 30-nm-thick gold electrodes are deposited.The results of performing XPS and Auger electron spectroscopy on samples before and after annealing show that the p-doping effect is due to the oxidation of selenide atoms,during which the gold acts as a critical catalytic element.This method is also shown to be valid for other 2D selenides including WSe_(2)and MoSe_(2),and the present findings offer new avenues for enriching the electrical properties of 2D selenides by means of annealing.
基金supported by the National Natural Science Foundation of China(Nos.22066017,22272070,W2412067,and 22471155)Jiangxi Province“double thousand plan”project.
文摘The fabrication of efficient and stable catalysts to accelerate the kinetics of the hydrogen evolution reaction(HER)is a crucial step in the development of sustainable energy production.The structural design of Pt-based catalysts with efficient atom utilization remains a pivotal factor in the continued advancement of HER catalysts.In this work,we synthesized phosphorylated Mo-based particles embedded in P-doped carbon materials for the optimized loading of platinum nanoparticles(Pt/Mo-P@C).Theoretical results indicate that the catalytic efficacy of the materials can be enhanced by altering the electronic structure of Pt nanoparticles through the precise formation of Pt-Mo bond and multiple heterostructures.The catalysts exhibited exceptional mass activity after low-temperature reduction,achieving a current density of 100 mA·cm−2 at 54.4 mV,which is lower than that of the commercial Pt/C catalyst.Furthermore,the mass activity of the main catalyst was 6.7 times greater than that of the commercial Pt/C catalyst at an overpotential of 50 mV.
文摘The industrial implementation of Solar-driven photocatalysis is hampered by inefficient charge separation,poor reusability and hard retrieval of powdery catalysts.To conquer these drawbacks,a self-floating S-scheme Bi_(4)O_(5)Br_(2)/P-doped C_(3)N_(4)/carbon fiber cloth(BB/PN/CC)composed of carbon fibers(CC)as the core and Bi_(4)O_(5)Br_(2)/P-doped C_(3)N_(4)(BB/PN)nanosheets as the shell was constructed as a competent,recyclable cloth-shaped photocatalyst for safe and efficient degradation of aquacultural antibiotics.The BB/PN/CC fabric achieves an exceptional tetracycline degradation rate constant of 0.0118 min‒1,surpassing CN/CC(0.0015 min^(‒1)),BB/CC(0.0066 min^(‒1))and PN/CC(0.0023 min^(‒1))by 6.9,0.8 and 4.1 folds,respectively.Beyond its catalytic prowess,the photocatalyst’s practical superiority is evident in its effortless recovery and environmental adaptability.The superior catalytic effectiveness stems from the S-scheme configuration,which retains the maximum redox capacities of the constituent BB and PN while enabling efficient spatial detachment of photo-carriers.X-ray photoelectron spectroscopy(XPS),in-situ XPS,and electron paramagnetic resonance analyses corroborate the S-scheme mechanism,revealing electron accumulation on PN and hole retention on BB under illumination.Density functional theory calculations further confirm S-scheme interfacial charge redistribution and internal electric field formation.This study advances the design of macroscopic S-scheme heterojunction photocatalysts for sustainable water purification.
基金financially supported by the National Natural Science Foundation of China (Nos.U2002212,52102058,52204414,52204413,and 52204412)the National Key R&D Program of China (Nos.2021YFC1910504,2019YFC1907101,2019YFC1907103,and 2017YFB0702304)+7 种基金the Key R&D Program of Ningxia Hui Autonomous Region,China (Nos.2021BEG01003 and2020BCE01001)the Xijiang Innovation and Entrepreneurship Team,China (No.2017A0109004)the Macao Young Scholars Program (No.AM2022024),Chinathe Beijing Natural Science Foundation (Nos.L212020 and 2214073),Chinathe Guangdong Basic and Applied Basic Research Foundation,China (Nos.2021A1515110998 and 2020A1515110408)the China Postdoctoral Science Foundation (No.2022M710349)the Fundamental Research Funds for the Central Universities,China (Nos.FRF-BD-20-24A,FRF-TP-20-031A1,FRF-IC-19-017Z,and 06500141)the Integration of Green Key Process Systems MIIT and Scientific and Technological Innovation Foundation of Foshan,China(Nos.BK22BE001 and BK21BE002)。
文摘Exclusive responsiveness to ultraviolet light (~3.2 eV) and high photogenerated charge recombination rate are the two primary drawbacks of pure TiO_(2). We combined N-doped graphene quantum dots (N-GQDs), morphology regulation, and heterojunction construction strategies to synthesize N-GQD/N-doped TiO_(2)/P-doped porous hollow g-C_(3)N_(4) nanotube (PCN) composite photocatalysts (denoted as G-TPCN). The optimal sample (G-TPCN doped with 0.1wt% N-GQD, denoted as 0.1% G-TPCN) exhibits significantly enhanced photoabsorption, which is attributed to the change in bandgap caused by elemental doping (P and N), the improved light-harvesting resulting from the tube structure, and the upconversion effect of N-GQDs. In addition, the internal charge separation and transfer capability of0.1% G-TPCN are dramatically boosted, and its carrier concentration is 3.7, 2.3, and 1.9 times that of N-TiO_(2), PCN, and N-TiO_(2)/PCN(TPCN-1), respectively. This phenomenon is attributed to the formation of Z-scheme heterojunction between N-TiO_(2) and PCNs, the excellent electron conduction ability of N-GQDs, and the short transfer distance caused by the porous nanotube structure. Compared with those of N-TiO_(2), PCNs, and TPCN-1, the H2 production activity of 0.1%G-TPCN under visible light is enhanced by 12.4, 2.3, and 1.4times, respectively, and its ciprofloxacin (CIP) degradation rate is increased by 7.9, 5.7, and 2.9 times, respectively. The optimized performance benefits from excellent photoresponsiveness and improved carrier separation and migration efficiencies. Finally, the photocatalytic mechanism of 0.1% G-TPCN and five possible degradation pathways of CIP are proposed. This study clarifies the mechanism of multiple modification strategies to synergistically improve the photocatalytic performance of 0.1% G-TPCN and provides a potential strategy for rationally designing novel photocatalysts for environmental remediation and solar energy conversion.
基金financially supported by Jiangsu Province Key Laboratory of Biomass Energy and Materials(No.JSBEM-S-202101)the Young Top Talent Program of Zhongyuan-Yingcai-Jihua(No.30602674)+1 种基金the Top-Notch Talent Program of Henan Agricultural University(No.30501034)the National Natural Science Foundation of China(Nos.31901272 and No.22279118)。
文摘Catalysts for oxygen conversion play an important role in energy storage and conversion technologies such as metal-air batteries.Developing highly active stable,and low-cost catalysts is critical for further implementation of the above technologies.Herein,an efficien oxygen electrocatalyst with Co_(2)P nanoparticles(NPs)coupling onto N,P-doped porous carbon nanosheets(Co_(2)P@NPAC)derived from cotton stalk is successfully designed and prepared via activation,hydrothermal treatment,and pyrolysis procedure.The excellent properties of electrical conductivity,mass transfer,and synergistic integration between Co_(2)P and N,P-doped carbon endow Co_(2)P@NPAC composite with superior oxygen reduction reaction/oxygen evolution reaction(ORR/OER)performance.Co_(2)P@NPAC catalyst achieves ORR activity with half-wave potential of 0.85 V and high OER activity with overpotential of 261 mV at 10 mA·cm^(-2).The flexible Zn-air batteries(ZABs)based on Co_(2)P@NPAC catalyst revea outstanding performances with a high open-circuit voltage(1.38 V),a peak power density of(75 mW·cm^(-2)),and a low charge-discharge voltage gap(0.74 V,~200 cycles)The flexible ZABs express the stable discharge-charge voltage gap at various bending states.This work provides interesting inspiration for the ingenious design of efficien carbon electrocatalysts from biomass with potential application of energy storage and conversion devices.
基金the National Nature Science Foundation of China(No.22304021)National Key Research and Development Project(No.2022YFA1505300)Sichuan Department of Science and Technology Program of China(No.2022YFG0312)for financial support。
文摘It is necessary to adopt a specific strategy to construct an efficient and low-cost transition metal-based composite to replace the precious metal-based electrocatalyst for OER catalytic processes.In this work,a beaded stream-like N and P-codoped carbon-coated Fe_(3)O_(4)nanocomposite(N,P-Fe_(3)O_(4)@C)is derived from MIL-88A by two-step annealing.The unique 3D nanostructure and amorphous N-doped carbon layer enlarge the number of active sites,and P doping changes the pathway from AEM to LOM.The synergistic effect of these factors results in N,P-Fe_(3)O_(4)@C presenting excellent OER catalytic activity with an overpotential of 201 mV(η10),a Tafel slope of 57.1 mV/dec and stable operation for 100 h(the current density is 10 mA/cm^(2)).Density functional theory calculations and electrochemical tests reveal that the P doping enhances the overlap of Fe 3d orbital bands and O 2p orbitals,and thus significantly increases the metaloxygen covalency,triggering the pathway transition from AEM to LOM.This work provides a new way to construct more efficient transition metal-based composite carbon materials.
基金supported by the National Natural Science Foundation of China(Nos.21777034 and 21606052)Natural Science Foundation of Guangdong Province(2020A1515010344)+4 种基金Science and Technology Innovation Project of Guangdong Province College Students(201811656019)Guangdong Province Universities and Colleges Pearl River Scholar Funded Scheme(2019)Guangdong Basic and Applied Basic Research Foundation(2019A1515011249)Key Research Project of Natural Science of Guangdong Provincial Department of Education(2019KZDXM010)the program for Innovative Research Team of Guangdong University of Petrochemical Technology。
文摘Hydrogen production by photolysis of water by sunlight is an environmentally-friendly preparation technology for renewable energy.Graphitic carbon nitride(g-C3N4),despite with obvious catalytic effect,is still unsatisfactory for hydrogen production.In this work,phosphorus element is incorporated to tune g-C3N4's property through calcinating the mixture of g-C3N4 and Na H2PO2,sacrificial agent and co-catalyst also been supplied to help efficient photocatalytic hydrogen production.Phosphorus(P)doped g-C3N4 samples(PCN-S)were prepared,and their catalytic properties were studied.X-ray diffraction(XRD),X-ray photoelectron spectroscopy(XPS),scanning electron microscopy(SEM)and ultraviolet diffuse reflection(UV-DRS)were used to study their structures and morphologies.The results show that the reaction rate of PCN-S is 318μmol·h^-1·g^-1,which is 2.98 times as high as pure carbon nitride nanosheets(CN)can do.Our study paves a new avenue,which is simple,environment-friendly and sustainable,to synthesize highly efficient P doping g-C3N4 nanosheets for solar energy conversion.
基金supported by the National Natural Science Foundation of China(21421001,21573115)
文摘Chemically modified carbonaceous materials have attained utmost attention in the fields of renewable energy storage and conversion,due to the controllable physicochemical properties,tailorable micro-/nanostructures,and respectable stability.Herein,P-doped mesoporous carbons were synthesized by using F127 as the soft template,organophosphonic acid as the P source and phenolic resin as the carbon source.Small amounts of iron species were introduced to act as a graphitization catalyst.The synthesized carbons exhibit the well-defined wormhole-like pore structure featuring high specific surface area and homogenously doped P heteroatoms.Notably,introducing iron species during the synthesis process can optimize the textural properties and the degree of graphitization of carbon materials.The doping amount of P has an important effect on the porous structure and the defect degree,which correspondingly influence the active sites and the oxygen reduction reaction(ORR)activity.The resultant material presents superior catalytic activity for the ORR,together with remarkably enhanced durability and methanol tolerance in comparison with the commercial Platinum catalyst,demonstrating the possibility for its use in electrode materials and electronic nanodevices for metal-air batteries and fuel cells.
基金the Natural Science Foundation of Shandong Province(No.ZR2019QEM001)the Guangdong Basic and Applied Basic Research Foundation(No.2019A1515111089)the National Natural Science Foundation of China(Grant No.22005178)。
文摘We report for the first time a Na-ion battery anode material composed of P-doped CoSe_(2)nanoparticles(P-CoSe_(2))with the size of 5–20 nm that are uniformly embed in a 3 D porous honeycomb-like carbon network.High rate capability and cycling stability are achieved simultaneously.The honeycomb-like carbon network is rationally designed to support high electrical conductivity,rapid Na-ion diffusion as well as the accommodation of the volume expansion from the active P-CoSe_(2)nanoparticles.In particular,heteroatom P-doping within CoSe_(2)introduces stronger P-Co bonds and additional P-Se bonds that significantly improve the structure stability of P-CoSe_(2)for highly stable sodiation/desodiation over long-term cycling.P-doping also improves the electrical conductivity of the CoSe_(2)nanoparticles,leading to highly elevated electrochemical kinetics to deliver high specific capacities at high current densities.Benefiting from the unique nanostructure and atomic-level P-doping,the P-CoSe_(2)(2:1)/C anode delivers an excellent cycle stability with a specific capacity of 206.9 mA h g^(-1)achieved at 2000 mA g^(-1)after 1000 cycles.In addition,this material can be synthesized using a facile pyrolysis and selenization/phosphorization approach.This study provides new opportunities of heteroatom doping as an effective method to improve the cycling stability of Na-ion anode materials.
基金financially supported by the National Natural Science Foundation of China (Nos. 52122308, 21905253,51973200, U21A20329)the Natural Science Foundation of Henan(No. 202300410372)+1 种基金the Key Scientific Research Projects of Higher Education Institutions in Henan ProvinceChina (No.21A150054)。
文摘Graphite carbon nitride(g-C_(3)N_(4)) is a promising non-metal photocatalyst for photocatalytic hydrogen production, but its performance is still limited due to sluggish charges separation and low utilization of light.In this work, P-doped and N-doped carbon dots(NCDs) supported g-C_(3)N_(4)were successfully prepared via hydrothermal and polymerization reactions. The sub-bandgap formed by P-doping enhances the utilization of visible light, and the high electron density of P sites is conducive to the trapping of holes. NCDs also improve light utilization and, more importantly, act as electron acceptors and transporters to promote electron transport. The built-in electric field formed by the synergy of P-doping and NCDs-loading greatly promotes the separation of charges. The PCN/NCDs showed a significantly improved hydrogen evolution activity of 3731 μmol h^(-1)g^(-1), which was 6.7 times that of pure carbon nitride(560 μmol h^(-1)g^(-1)). This strategy may be generalized to the design of g-C_(3)N_(4)-based photocatalysts, facilitating the separation of charges for enhanced catalytic activity.
文摘Four kinds of polythiophenes have been doped with CH3SO3H in CHCl3 under air,oxygen,and nitrogen. In the doping of two types of poly(3-hexylthiophene)s,P3HexTh(Zn/Ni)and P3HexTh(Fe)with different contents of a head-to-tail unit,the p-doping occurs at a similar rate.The reaction between poly(3-dodecylthiophene),P3DodTh,and the acid takes place more rapidly.P3OBuTh with a butoxy substituent undergoes more facile p-doping and receives photochemical reaction with CHCl3,and this reaction obeys a pseudo-first-order rate law with a rate constant kobs of 1.42×10-5s-1at room tempera- ture.
基金supported by National Natural Science Foundation of China(Nos.52472194,52101243)Natural Science Foundation of Guangdong Province,China(No.2023A1515012619)the Science and Technology Planning Project of Guangzhou(No.202201010565)。
文摘Owing to the advantages of high energy density,low cost,abundant sulfur reserves and environmentally friendly nature,lithium-sulfur batteries(LSBs)were considered as one of the potential candidates of energy storage devices for the next generation.However,the significant challenges in this area stem from the sluggish reaction kinetics of the insoluble Li_(2)S product and the capacity degradation triggered by the severe shuttle effect of polysulfides.It has been firmly established through numerous studies that modifying separators is an effective approach to enhance the properties of LSBs by facilitating the catalytic kinetic conversion and chemical adsorption of lithium polysulfides(Li PSs).In this work,we report a straightforward method for fabrication of the phosphorus doped porous CeO_(2)(P-CeO_(2))as separator modifier to accelerate the catalytic kinetic conversion of polysulfides and effectively inhibit the shuttle effect in LSBs.Through coin batteries tests,P-CeO_(2)modified PP separator(P-CeO_(2)//PP)exhibits remarkable electrochemical performance.It demonstrates a high initial capacity of 1180 mAh/g at 0.5 C,surpassing the performance of the bare CeO_(2)//PP separator.Furthermore,the P-CeO_(2)//PP separator demonstrates enhanced cycling stability,with a low-capacity fading rate of only 0.048%per cycle over 1000 cycles at 2 C.In compared with bare CeO_(2)//PP,P-CeO_(2)//PP exhibits high redox peak current,enhanced adsorption property of Li_(2)S_(6)and early Li_(2)S precipitation.These results highlight the superior performance of the P-CeO_(2)//PP separator compared to the bare CeO_(2)//PP separator.Hence,this research presents a successful strategy for the modification of LIBs separator with improved electrochemical performance and cycle stability.
基金financially supported by Natural Science Foundation of Shandong Province(No.ZR2024QB415)。
文摘The biomass electrochemical oxidation coupled with hydrogen evolution reaction has received widespread attention due to its carbon-neutral and sustainable properties.The electrosynthesis of 2,5-furanodicarboxylic acid(FDCA)from 5-hydroxymethylfurfural(HMF)oxidation is one of the most promising means for the production of bioplastic monomers.In this work,we constructed a novel P-doped Ni_(3)S_(2)and Ni heterojunction on nickel foam(P-Ni_(3)S_(2)/Ni/NF)using electrodeposition methods and thermal sulfuration techniques as a bifunctional catalyst for the simultaneous anodic oxidation of HMF to FDCA(HMFOR)and the cathodic hydrogen evolution reaction(HER).On one hand,the synergistic promotion of P doping and the heterojunction of Ni_(3)S_(2)and Ni accelerated electron transfer,and on the other hand,the structure of three-dimensional microsphere stacking on NF surface to form macropores enhances the exposure of catalytically active sites.The prepared P-Ni_(3)S_(2)/Ni/NF exhibited remarkable performance with high HMF conversion(99.2%),FDCA yield(98.1%),and Faraday efficiency(98.8%),and excellent stability with good product selectivity for 7 consecutive cycles,which stands at a higher level than majority of previously published electrocatalysts.Furthermore,P-Ni_(3)S_(2)/Ni/NF also shows a significant response in HER.By using HMFOR and HER as the anodic reaction and cathodic reaction,respectively,the biomass upgrading and hydrogen production can be carried out simultaneously.The synthesized P-Ni_(3)S_(2)/Ni/NF only need a voltage of 1.31V to achieve a current density of 10mA/cm^(2)in a two-electrode system of HMFOR and HER,which is much lower than that of 1.48 V in OER and HER process,thus potentially reducing the cost of this process.
基金the financial supports provided by the National Natural Science Foundation of China(21871164)Young Scholars Program of Shandong University(No.2017WLJH15)+2 种基金the China Postdoctoral Science Foundation(Nos.2017M610419 and 2018T110680)the Special Fund for Postdoctoral Innovation Program of Shandong Province(No.201701003)the Taishan Scholar Project of Shandong Province(No.ts201511004)
文摘Lithium–sulfur(Li–S)batteries have attracted much attention due to their ultrahigh theoretical specific capacity.However,serious capacity attenuation caused by shuttle effect still inhibits the performance improvement.Herein,a modified separator consists of the few-layer graphene as a highly conductive network and stable scaffold to support P-doped boron nitride(denoted as BN-P@GO)as the functional interlayer of Li–S batteries.The cell with the interlayer provides an initial discharge capacity as high as1045.3 mAh g^-1,and retains a high reversible capacity of 728.7 mAh g^-1 at 1 C after 500 cycles with a capacity decay of 0.061%per cycle.Moreover,the rate capability is also superior to cells with BN@GO or BN-P interlayers,i.e.reversible capcity of 457.9 mAh g^-1 even at 3 C.The excellent electrochemical performance is ascribed to the synergistic effect of physical barrier and chemical adsorption for dissolved polysulfides provided by the modified layer.Furhtermore,it also mitigates the polarization and promotes kinetic reactions of the cells.This work provides a concise and effective method for commercialization of lithium–sulfur batteries.
基金supported by the National Natural Science Foundation of China(51672113)QingLan Project Foundation of Jiangsu Province(201611)~~
文摘g-C3N4 is a metal-free semiconductor and a potential candidate for photocatalytic H2 production,however,the drawbacks,rapid recombination rate and limited migration efficiency of photogenerated carriers,restrict its photocatalytic activity.Herein,Co(II)as a hole cocatalyst modified P-doped g-C3N4 were successfully prepared to ameliorate the separation efficiency of photoinduced carriers and enhance the photocatalytic hydrogen production.The photocatalytic results demonstrated that the P-doped g-C3N4(PCN)exhibited higher photocatalytic activity compared with pure g-C3N4,while Co(II)/PCN photocatalyst exhibited further enhancement of photocatalytic performance.The proposed possible mechanism based on various characterizations is that P-doping can modulate the electronic structure of g-C3N4 to boost the separation of photogenerated-e-and h+;while the synergistic effect of both Co(II)(as hole cocatalyst)and Pt(as electron cocatalyst)can not only lead to the directional shunting of photogenerated e+-h?pairs,but further accelerate the photogenerated electrons transfer to Pt in order to join the photocatalytic reduction process for hydrogen evolution.As a result,the transportation and separation of photoinduced carriers were accelerated to greatest extent in the Pt/Co(II)/PCN photocatalyst.
基金the National Natural Science Foundation of China(Nos.51772085 and U1830138)Hunan Provincial Innovation Foundation for Postgraduate(No.CX20190311)
文摘Self-assembled nanostructure arrays integrating the advantages of the intrinsic characters of nanostructure as well as the array stability are appealing in advanced materials.However,the precise bottom-up synthesis of nanostructure arrays without templates or substrates is quite challenging because of the general occurrence of homogeneous nucleation and the difficult manipulation of noncovalent interactions.Herein,we first report the precisely manipulated synthesis of well-defined louver-like P-doped carbon nitride nanowire arrays(L-PCN)via a supramolecular self-assembly method by regulating the noncovalent interactions through hydrogen bond.With this strategy,CN nanowires align in the outer frame with the separation and spatial location achieving ultrastability and outstanding photoelectricity properties.Significantly,this self-assembly L-PCN exhibits a superior visible light-driven hydrogen evolution activity of 1872.9μmol h^−1 g^−1,rendering a^25.6-fold enhancement compared to bulk CN,and high photostability.Moreover,an apparent quantum efficiency of 6.93%is achieved for hydrogen evolution at 420±15 nm.The experimental results and first-principles calculations demonstrate that the remarkable enhancement of photocatalytic activity of L-PCN can be attributed to the synergetic effect of structural topology and dopant.These findings suggest that we are able to design particular hierarchical nanostructures with desirable performance using hydrogen-bond engineering.
基金support from the National Natural Science Foundation of China(Nos.61701386,21975196,51771140)the Young Star Project of Science and Technology of Shaanxi Province(No.2019KJXX-033)the Natural Science Basic Research Plan in Shaanxi Province of China(No.2022JM-358).
文摘Structural design and elemental doping are research hotspots for the preparation of lightweight absorbers with high absorption performance and low filling ratio.Herein,a P-doped hydrangea-like layered compos-ite(Co_(2)P/Ni_(2)P@C)encapsulated with Ni-LDH was successfully synthesized by solvothermal method fol-lowed by phosphorization.The defects generated by P doping and the generation of multilayered nonuni-form interfaces enhance the dielectric loss induced by polarization.Simultaneously,the magnetic phos-phides induce magnetic loss and modulate the dielectric properties of the carbon matrix to enhance the conductive loss.The multilayered hollow structure of this composite promotes the scattering and reflec-tion of electromagnetic waves and optimizes the impedance characteristics.As a result,the multilayered hollow Co_(2)P/Ni_(2)P@C composite exhibits an optimum reflection loss value(RL)of–64.6 dB at 15.1 GHz with a thickness of 2 mm and a filler ratio of only 10 wt%.The radar cross-section(RCS)attenuation further demonstrates that the material can dissipate microwave energy in practical applications.Overall,this work provides an effective development strategy for the design of multilayered high-performance electromagnetic wave(EMW)absorbers doped with strongly polarized elements.
基金supported by the National Key R&D Program of China(2023YFD1701504)the 2115 Talent Development Program of China Agricultural University Fund(1011-00109018)the Beijing Innovation Team of the Modern Agricultural Research System(BAIC08-2023-FQ02)。
文摘Optimizing the intrinsic activity of non-noble metal by precisely tailoring electronic structure offers an appealing way to construct cost-effective catalysts for selective biomass valorization.Herein,we reported a P-doping bifunctional catalyst(Ni-P/mSiO_(2))that achieved 96.6%yield for the hydrogenation rearrangement of furfural to cyclopentanone at mild conditions(1 MPaH_(2),150°C).The turnover frequency of Ni-P/mSiO_(2)was 411.9 h^(-1),which was 3.2-fold than that of Ni/mSiO_(2)(127.2 h^(-1)).Detailed characterizations and differential charge density calculations revealed that the electron-deficient Niδ+species were generated by the electron transfer from Ni to P,which promoted the ring rearrangement reaction.Density functional theory calculations illustrated that the presence of P atoms endowed furfural tilted adsorb on the Ni surface by the C=O group and facilitated the desorption of cyclopentanone.This work unraveled the connection between the localized electronic structures and the catalytic properties,so as to provide a promising reference for designing advanced catalysts for biomass valorization.
基金funded by the National Natural Science Foundation of China(Grant Nos.62322410,52272168,52161145404,81974530,and 82271721)the Fundamental Research Funds for the Central Universities(Grant No.WK3500000009)+1 种基金the International Projects of the Chinese Academy of Science(CAS)under Grant No.211134KYSB20210011Hubei Provincial Science and Technology Innovation Talents and Services Special Program(Grant No.2022EHB039)。
文摘Photosensors with versatile functionalities have emerged as a cornerstone for breakthroughs in the future optoelectronic systems across a wide range of applications.In particular,emerging photoelectrochemical(PEC)-type devices have recently attracted extensive interest in liquid-based biosensing applications due to their natural electrolyte-assisted operating characteristics.Herein,a PEC-type photosensor was carefully designed and constructed by employing gallium nitride(GaN)p-n homojunction semiconductor nanowires on silicon,with the p-GaN segment strategically doped and then decorated with cobalt-nickel oxide(CoNiO_(x)).Essentially,the p-n homojunction configuration with facile p-doping engineering improves carrier separation efficiency and facilitates carrier transfer to the nanowire surface,while CoNiO_(x)decoration further boosts PEC reaction activity and carrier dynamics at the nanowire/electrolyte interface.Consequently,the constructed photosensor achieves a high responsivity of 247.8 mA W^(-1)while simultaneously exhibiting excellent operating stability.Strikingly,based on the remarkable stability and high responsivity of the device,a glucose sensing system was established with a demonstration of glucose level determination in real human serum.This work offers a feasible and universal approach in the pursuit of high-performance bio-related sensing applications via a rational design of PEC devices in the form of nanostructured architecture with strategic doping engineering.
文摘The electronic structure of catalytic active sites can be influenced by modulating the coordination bonding of the central single metal atom,but it is difficult to achieve.Herein,we reported the single Zn-atom incorporated dual doped P,N carbon framework(Zn-N_(4)P/C)for ORR via engineering the surrounding coordination environment of active centers.The Zn-N_(4)P/C catalyst exhibited comparable ORR activity(E_(1/2)=0.86 V)and significantly better ORR stability than that of Pt/C catalyst.It also shows respectable performance in terms of maximum peak power density(249.6 mW cm^(-2)),specific capacitance(779 mAh g^(-1)),and charge-discharge cycling stability for 150 hours in Zn-air battery.The high catalytic activity is attributed to the uniform active sites,tunable electronic/geometric configuration,optimized intrinsic activity,and faster mass transfer during ORR-pathway.Further,theoretical results exposed that the Zn-N_(4)P configuration is more electrochemically active as compared to Zn-N_(4) structure for the oxygen reduction reaction.
