By simplifying catalyst-product separation and reducing phosphorus waste,heterogeneous hydroformylation offers a more sustainable alternative to homogeneous processes.However,heterogeneous hydroformylation catalysts d...By simplifying catalyst-product separation and reducing phosphorus waste,heterogeneous hydroformylation offers a more sustainable alternative to homogeneous processes.However,heterogeneous hydroformylation catalysts developed thus far still suffer from the issues of much lower activity and metal leaching,which severely hinder their practical application.Here,we demonstrate that incorporating phosphorus(P)atoms into graphitic carbon nitride(PCN)supports facilitates charge transfer from Rh to the PCN support,thus largely enhancing electronic metal-support interactions(EMSIs).In the styrene hydroformylation reaction,the activity of Rh_(1)/PCN single-atom catalysts(SACs)with varying P contents exhibited a volcano-shaped relationship with P doping,where the Rh_(1)/PCN SAC with optimal P doping showed exceptional activity,approximately 5.8-and 3.3-fold greater than that of the Rh_(1)/g-C_(3)N_(4)SAC without P doping and the industrial homogeneous catalyst HRh(CO)(PPh_(3))_(3),respectively.In addition,the optimal Rh_(1)/PCN SAC catalyst also demonstrated largely enhanced multicycle stability without any visible metal aggregation owing to the increased EMSIs,which sharply differed from the severe metal aggregation of large nanoparticles on the Rh_(1)/g-C_(3)N_(4)SAC.Mechan-istic studies revealed that the enhanced catalytic performance could be attributed to electron-deficient Rh species,which reduced CO adsorption while simultaneously promoting alkene adsorption through increased EMSIs.These findings suggest that tuning EMSIs is an effective way to achieve SACs with high activity and durability.展开更多
The development of high-performance lithium-ion batteries(LIBs)hinges on searching for advanced anode materials with large specific capacities as well as high cycling stability.However,traditional graphite anodes have...The development of high-performance lithium-ion batteries(LIBs)hinges on searching for advanced anode materials with large specific capacities as well as high cycling stability.However,traditional graphite anodes have not met the demand for higher energy storage owing to the deficiency of low lithium storage capacity.In the current work,we focus on designing one composite anode material with multiscale porous(MP)structure and phosphorus(P)doping.The coupling effects of three-dimensional(3D)interconnected skeleton,hollow pore channels,and P doping can facilitate the electrolyte diffusion and the mass transfer,as well as accommodate the volume changes during lithiation/delithiation processes.As expected,the as-prepared MP-SiGeSnSbPAl composite exhibits superior lithium storage performance,achieving a specific capacity of 827.9 mAh/g after 150 cycles at 200 mA/g and maintaining the high capacity of 456.7 mAh/g after 400 cycles at 1 A/g.Contrastively,the corresponding surplus capacities are only 590.3 and 225.7 mAh/g for the non-doped counterparts,respectively.In particular,MP-SiGeSnSbPAl displays much more stable cycling performances under the measurement of high areal mass loading of~3 mg/cm^(2)and the full-cell tests with the lithium iron phosphate as the cathode.This work witnesses one scalable protocol for preparing multinary Si-based composite in terms of facile operation and high lithium storage performances.展开更多
Hydrogenated silicon carbide films (SiC:H) were deposited using the electron cyclotron resonance chemical vapour deposition (ECR-CVD) technique from a mixture of methane, silane and hydrogen, and using diborane and ph...Hydrogenated silicon carbide films (SiC:H) were deposited using the electron cyclotron resonance chemical vapour deposition (ECR-CVD) technique from a mixture of methane, silane and hydrogen, and using diborane and phosphine as doping gases. The effects of changes in the microwave power on the deposition rate and optical bandgap were investigated, and variations in the photoand dark-conductivities and activation energy were studied in conjunction with film analysis using the Raman scattering technique. In the case of boron-doped samples, the conductivity increased rapidly to a maximum, followed by rapid reduction at high microwave power. The ratio of the photo- to dark-conductivity (σph/σd) peaked at microwave power of ~600 W. Under conditions of high microwave power, Raman scattering analysis showed evidence of the formation and increase in the silicon microcrystalline and diamond-like phases in the films, the former of which could account for the rapid increase and the latter the subsequent decrease in the conductivity.In the case of phosphorusdoped SiC:H samples, it was found that increase in the microwave power has the effect of enhancing the formation of the silicon microcrystalline phase in the films which occurred in correspondence to a rapid increase in the conductivity and reduction in the activation energy The conductivity increase stabilised in samples deposited at microwave power exceeding 500 W probably as a result of dopant saturation. Results from Raman scattering measurements also showed that phosphorus doping had the effect of enhancing the formation of the silicon microcrystals in the film whereas the presence of boron had the effect of preserving the amorphous structure.展开更多
Correction to:Rare Met.https://doi.org/10.1007/s12598-021-01864-4 In the original publication,the affiliation of the 5th author(Corresponding author)was published incorrectly.The correct affiliation is given in this C...Correction to:Rare Met.https://doi.org/10.1007/s12598-021-01864-4 In the original publication,the affiliation of the 5th author(Corresponding author)was published incorrectly.The correct affiliation is given in this Correction.The original publication has been corrected.展开更多
Titanium dioxide is considered to be promising anode for sodium-ion batteries due to stable structure during the charge/discharge process.However,its practical application is hindered by the slow electron/ion transpor...Titanium dioxide is considered to be promising anode for sodium-ion batteries due to stable structure during the charge/discharge process.However,its practical application is hindered by the slow electron/ion transport.Herein,phosphorus-doped anatase TiO_(2) nanoparticles with oxygen vacancies are successfully synthesized and utilized as high-performance sodium-storage materials.The dual strategy of phosphorus-doping and oxygen vacancies can concurrently boost electronic conductivity and adjust ion diffusion kinetics.They significantly contribute to the improved rate performance(167 mAh·g^(-1) at 20.0C)and stable cycling(95.9%after 2000 cycles at 20.0C).The proposed dual strategy can be potentially used to improve other oxide anodes for rechargeable batteries.展开更多
The electrolysis of water into hydrogen and oxygen provides an effective means of storing electrical energy indirectly.The current challenge is to design an optimal catalyst that exhibits low overpotentials,long-term ...The electrolysis of water into hydrogen and oxygen provides an effective means of storing electrical energy indirectly.The current challenge is to design an optimal catalyst that exhibits low overpotentials,long-term stability,universal availability,and only uses inexpensive materials.Herein,a Co3O4nanoflower/stainless steel(P-Ov-CO_(3)O_(4)/SS) catalyst with both oxygen vacancies(Ovs) and phosphorus doping was perfectly prepared via a simple three-step method.The Ovs promoted charge transfer and accelerated the electrocatalysis,while P finely tuned the surface charge state.This resulted in numerous active sites for catalysis,and the synergistic effect of phosphorus doping and oxygen vacancies was finely demonstrated.The resultant electrocatalyst exhibited low hydrogen evolution overpotentials of 118 mV(-10 mA·cm^(-2)) and 242(-200 mA·cm^(-2)),as well as oxygen evolution overpotentials of 327 mV(100 mA·cm^(-2)) and 370 mV(200 mA·cm^(-2)),owing to the excellent synergistic effect of the Ovs and low-temperature phosphating.Moreover,P-Ov-Co_(3)O_(4)/SS//P-Ov-Co_(3)O_(4)/SS exhibited a low water splitting voltage of 1.681 V at 20 mA.cm-2.These findings will enable the synthesis of novel high-performance electrocatalysts for overall water splitting.展开更多
Phosphorus-doped carbon nanospheres without any metal residues were synthesized and characterized. The results revealed that the doping phosphorus atoms could significantly improve the electrocatalytic activity of gra...Phosphorus-doped carbon nanospheres without any metal residues were synthesized and characterized. The results revealed that the doping phosphorus atoms could significantly improve the electrocatalytic activity of graphitic carbon for the oxygen-reduction reaction （ORR） both in acidic and alkaline media, and the materials exhibited high electrocatalytic activity, long-term stability, and excellent tolerance to crossover effects especially in alkaline media. Quantum mechanics calculations with the density functional theory demonstrated that the changes in charge density and energetic characteristics of frontier orbitals for the P-doped graphene sheet could facilitate the ORR.展开更多
Compact supercapacitors(SCs)have attracted attention for their great potential to replace bulky aluminum electrolytic capacitors(AECs)in alternating current(AC)line filtering applications.Herein,the fabrication of a h...Compact supercapacitors(SCs)have attracted attention for their great potential to replace bulky aluminum electrolytic capacitors(AECs)in alternating current(AC)line filtering applications.Herein,the fabrication of a high-frequency SC is reported using Ketjen black(KB)nanoparticles doped with phosphorus(P)to achieve a high areal capacitance of up to 2.26 mF cm^(-2)along with a high-rate capability,with a phase angle of-80.2°at 120 Hz.The high performance of the phosphorus-doped KB(designated PKB)SC with a 6 M KOH aqueous electrolyte is associated with its increased surface wettability and additional capacitive sites provided by the P-doping.Density functional theory(DFT)calculations further indicate that the P-doping enhances the interactions between the electrolyte ions and the carbon surface,thus leading to an improved electrochemical performance.These results suggest that the P-doped carbonbased SC could be highly favored in replacing conventional AECs in various high-frequency electronic devices.展开更多
Phosphorus-doped mesoporous carbons(PMCs)were prepared using a self-doping and self-templating approach via direct pyrolysis of sodium phytate(C_(6)H_(17)NaO_(24)P_(6)).The one-pot method allows simultaneous carboniza...Phosphorus-doped mesoporous carbons(PMCs)were prepared using a self-doping and self-templating approach via direct pyrolysis of sodium phytate(C_(6)H_(17)NaO_(24)P_(6)).The one-pot method allows simultaneous carbonization and P doping,eliminating the need for pre-synthesis or post-activation treatment.The C_(6)H_(17)NaO_(24)P_(6)is the source of both carbon and phosphorus,and the nano-Na_(4)P_(2)O_(7)particles produced during pyrolysis act as hard templates for the honeycomb mesoporous structure with high specific surface area(884–827m^(2)/g),large mesopore volume ratio(67%–75%)and rich phosphorus content(0.53–2.34 at%).As electrodes of supercapacitors in 6 mol/L KOH,the PMCs showed outstanding performance with a high capacitance of 202 F/g and excellent rate performance of 148 F/g at 30 A/g.In addition,the PMCs-based symmetrical supercapacitors can operate in an expanded working voltage of 0–1.6 V in 3mol/L H_(2)SO_(4)aqueous electrolytes with high-density energy of 11.8 Wh/kg.展开更多
Owing to their high theoretical specific capacity and low cost, lithium- and manganese-rich layered oxide (LMR) cathode materials are receiving increasing attention for application in lithium-ion batteries. However, p...Owing to their high theoretical specific capacity and low cost, lithium- and manganese-rich layered oxide (LMR) cathode materials are receiving increasing attention for application in lithium-ion batteries. However, poor lithium ion and electron transport kinetics plus side effects of anion and cation redox reactions hamper power performance and stability of the LMRs. In this study, LMR Li_(1.2)Mn_(0.6)Ni_(0.2)O_(2) was modified by phosphorus (P)-doping to increase Li+ conductivity in the bulk material. This was achieved by increasing the interlayer spacing of the lithium layer, electron transport and structural stability, resulting in improvement of the rate and safety performance. P^(5+) doping increased the distance between the (003) crystal planes from ~0.474 nm to 0.488 nm and enhanced the structural stability by forming strong covalent bonds with oxygen atoms, resulting in an improved rate performance (capacity retention from 38% to 50% at 0.05 C to 5 C) and thermal stability (50% heat release compared with pristine material). First-principles calculations showed the P-doping makes the transfer of excited electrons from the valence band to conduction band easier and P can form a strong covalent bond helping to stabilize material structure. Furthermore, the solid-state electrolyte modified P5+ doped LMR showed an improved cycle performance for up to 200 cycles with capacity retention of 90.5% and enhanced initial coulombic efficiency from 68.5% (pristine) or 81.7% (P-doped LMR) to 88.7%.展开更多
Diamond is known as the ultimate semiconductor owing to its excellent physical properties.However,the high difficulty of n-type doping and the poor electrical performance of n-type diamonds remain major challenges for...Diamond is known as the ultimate semiconductor owing to its excellent physical properties.However,the high difficulty of n-type doping and the poor electrical performance of n-type diamonds remain major challenges for the application of diamond semiconductor materials.In this paper,a high-pressure thermal diffusion method for the n-type doping of diamond,which utilizes high pressure to reduce the volume difference between phosphorus atoms and carbon atoms,is reported for the first time.This method can achieve efficient doping and ionization of phosphorus atoms at the lattice sites of diamond.The prepared phosphorus-doped diamond exhibited the lowest resistivity(2Ωcm)and highest electron concentration(2.27×10^(18) cm^(-3))observed in any known phosphorus-doped diamond single crystal at room temperature(300 K).The high-pressure thermal diffusion method provides an effective approach for diamond n-type doping,which may play an important role in the design and preparation of future diamond-based semiconductor devices.展开更多
Hematite(α-Fe_(2)O_(3))is a promising photoanode for photoelectrochemical(PEC)water splitting.However,the severe charge recombination and sluggish water oxidation kinetics extremely limit its use in photohydrogen con...Hematite(α-Fe_(2)O_(3))is a promising photoanode for photoelectrochemical(PEC)water splitting.However,the severe charge recombination and sluggish water oxidation kinetics extremely limit its use in photohydrogen conversion.Herein,a co-activation strategy is proposed,namely through phosphorus(P)doping and the loading of CoAl-layered double hydroxides(CoAl-LDHs)cocatalysts.Unexpectedly,the integrated system,CoAl-LDHs/P-Fe_(2)O_(3) photoanode,exhibits an outstanding photocurrent density of 1.56 mA/cm^(2) at 1.23 V(vs.reversible hydrogen electrode,RHE),under AM 1.5 G,which is 2.6 times of pureα-Fe_(2)O_(3).Systematic studies reveal that the remarkable PEC performance is attributed to accelerated surface OER kinetics and enhanced carrier separation efficiency.This work provides a feasible strategy to enhance the PEC performance of hematite photoanodes.展开更多
The inadequate performance of oxygen reduction reaction(ORR)catalysts hampers the development of proton exchange membrane fuel cells(PEMFCs).Herein,we proposed an approach to tackle this problem by modulating the chem...The inadequate performance of oxygen reduction reaction(ORR)catalysts hampers the development of proton exchange membrane fuel cells(PEMFCs).Herein,we proposed an approach to tackle this problem by modulating the chemical bond type of intermetallic Pt-based catalysts,using phosphorus(P)doped L1_(0)-PtFeGa_(0.1)/C(P-L1_(0)-PtFeGa_(0.1)/C)as a proof of concept.X-ray absorption spectroscopy(XAS)demonstrated that the doped P transferred electrons to Pt,and thus,modified the electronic structure of Pt,weakening the adsorption strength with oxygen-containing species.Therefore P-L1_(0)-PtFeGa_(0.1)/C showed 13 times mass activity(MA)compared with commercial Pt/C,with a decay of only 28%after 100,000 potential cycles.When equipped in the membrane electrode assembly,the P-L1_(0)-PtFeGa_(0.1)/C catalyst also exhibited a remarkable activity(MA=0.84 A mgPt^(−1)at 0.9 V)and stability(MA retention=72%and voltage loss=9 mVat 0.8 A cm^(−2)after 30,000 cycles),making it one of the best performers among recorded Pt-based catalysts.Theoretical studies demonstrated that the doping of P optimized the adsorption energy between Pt and oxygen intermediates through sp-d orbital interactions and prevented metal dissolution by forming stronger Pt-P covalent bonds compared with Pt–Pt bonds.展开更多
P‐doped TiO2 (PTIO) thin‐films with different P contents were prepared using a sol‐gel method. The thin‐film samples were characterized using various techniques. The photocatalytic activity was evaluated by decomp...P‐doped TiO2 (PTIO) thin‐films with different P contents were prepared using a sol‐gel method. The thin‐film samples were characterized using various techniques. The photocatalytic activity was evaluated by decomposing butyl benzyl phthalate under visible‐light irradiation. The results showed that the transformation of anatase to the rutile phase was inhibited and grain growth of TiO2 was prevented by P doping. The results confirm that the doped P atoms existed in two chemical forms, and those incorporated in the TiO2 lattice may play a positive role in photocatalysis. The high photocatalytic activities of the PTIO thin‐films may be the result of extrinsic absorption through the creation of oxygen vacancies, rather than excitation of the intrinsic absorption band of bulk TiO2 . The PTIO can be recycled with little depression of the photocatalytic activity. After six cycles, the photocatalytic activity of the PTIO film was still higher than 98%.展开更多
MoS_(2)is a promising electrocatalyst because of its natural abundance and outstanding electrochemical stability.However,the poor conductivity and low activity limit its catalytic performance;furthermore,MoS_(2)is una...MoS_(2)is a promising electrocatalyst because of its natural abundance and outstanding electrochemical stability.However,the poor conductivity and low activity limit its catalytic performance;furthermore,MoS_(2)is unable to satisfy the requirements of most industrial applications.In this study,to obtain a P-doped MoS_(2)catalyst with S vacancy defects,P is inserted into the MoS_(2)matrix via a solid phase ion exchange at room temperature.The optimal P-doping amount is 11.4 wt%,and the resultant catalyst delivers excellent electrocatalytic properties for the hydrogen evolution reaction(HER)and oxygen evolution reaction(OER)with the corresponding overpotentials of 93 and 316 mV at 10 mA cm^(-2) in an alkaline solution;these values surpass the overpotentials of most previously reported MoS_(2)-based materials.Theoretical calculations and results demonstrate that the synergistic effect of the doped P,which forms active centers in the basal plane of MoS_(2),and S vacancy defects caused by P doping intensifies the intrinsic electronic conductivity and electrocatalytic activity of the catalyst.Density functional theory calculations demonstrate that P optimizes the free energy of the MoS_(2)matrix for hydrogen adsorption,thereby considerably increasing the intrinsic activity of the doped catalyst for the HER compared with that observed from pristine MoS_(2).The enhanced catalytic activity of P-doped MoS_(2)for the OER is attributed to the ability of the doped P which facilitates the adsorption of hydroxyl and hydroperoxy intermediates and reduces the reaction energy barrier.This study provides a new environmentally friendly and convenient solid-phase ion exchange method to improve the electrocatalytic capability of two-dimensional transition-metal dichalcogenides in largescale applications.展开更多
Heteroatom doping is one of the most promising strategies toward regulating intrinsically sluggish electronic conductivity and kinetic reaction of transition metal oxides for enhancing their lithium storage.Herein,we ...Heteroatom doping is one of the most promising strategies toward regulating intrinsically sluggish electronic conductivity and kinetic reaction of transition metal oxides for enhancing their lithium storage.Herein,we designed phosphorus-doped NiMo0_(4) nanorods(P-NiMo0_(4))by using a facile hydrothermal method and subsequent low-temperature phosphorization treatment.Phosphorus doping played an indispensable role in significantly improving electronic conductivity and the Li+diffusion kinetics of NiMo0_(4) materials.Experimental investigation and density functional theory calculation demonstrated that phosphorus doping can expand the interplanar spacing and alter electronic structures of NiMo0_(4) nanorods.Meanwhile,the introduced phosphorus dopant can generate some oxygen vacancies on the surface of NiMo0_(4),which can accelerate Li+diffusion kinetics and provide more active site for lithium storage.As excepted,P-NiMo0_(4) electrode delivered a high specific capacity(1,130 mA·g^(-1) at 100 mA·g^(-1) after 100 cycles),outstanding cycling durability(945 mA·g^(-1) at 500 mA·g^(-1) over 200 cycles),and impressive rate performance(640 mA·g^(-1)at 2,000mA·g^(-1))for lithium ion batteries(LIBs).This work could provide a potential strategy for improving intrinsic conductivity of transition metal oxides as high-performance anodes for LIBs.展开更多
The controllable construction of non-noble metal based bifunctional catalysts with high activities towards oxygen reduction reaction(ORR)and oxygen evolution reaction(OER)is of great significance,but remains a challen...The controllable construction of non-noble metal based bifunctional catalysts with high activities towards oxygen reduction reaction(ORR)and oxygen evolution reaction(OER)is of great significance,but remains a challenge.Herein,we reported an effective method to synthesize cobalt-nitrogen doped mesoporous carbon-based bifunctional oxygen electrocatalyst with controllable phosphorus content(Co-N-P_(X)-MC,X=0.5,1.0,1.5,2.0).The mesoporous carbon substrate endowed the asprepared samples with more exposed active surface(236.50 m^(2)·g^(−1))and the most appropriate doping ratio of phosphorus had been investigated to be 1.5(Co-N-P1.5-MC).For ORR,Co-N-P1.5-MC exhibited excellent catalytic activity with more positive onset potential(1.01 V)and half-wave potential(0.84 V)than the other samples.For OER,Co-N-P1.5-MC also showed a low overpotential of 415 mV.Combining experimental results and density-functional theory(DFT)calculations,the outstanding bifunctional catalytic performance of Co-N-P1.5-MC was due to the synergistic cooperation between the P and N dopants,which could reduce the reaction barriers and was favorable for ORR and OER.Moreover,the Zn-air battery using Co-N-P1.5-MC as the cathode showed remarkable battery performance with high stability(could operate stably for over 160 h at 10 mA·cm^(−2))and maximum power density(119 mW·cm^(−2)),demonstrating its potential for practical applications.This work could provide significant enlightenment towards the design and construction of bifunctional oxygen electrocatalyst for next-generation electrochemical devices.展开更多
This work proposes a modified activated carbon support,with defects and heteroatoms(N,P-ACs)by nitrogen and phosphorus doping to load non-noble nickel to catalyze aromatic compound hydrogenation.The Ni/N,P-ACs-900(pre...This work proposes a modified activated carbon support,with defects and heteroatoms(N,P-ACs)by nitrogen and phosphorus doping to load non-noble nickel to catalyze aromatic compound hydrogenation.The Ni/N,P-ACs-900(prepared at 900℃)showed promising catalytic activity in liquid-phase 1,5-dinitronaphthalene hydrogenation with a 1,5-diaminonaphthalene yield of 95.8% under the mild condition of 100℃,which is comparable to the commercial Pd/C catalyst.The nitrogen species were burned off at 900℃,causing more defects for nickel metal loading,facilitating the interaction between the supports and the nickel metal,and resulting in highly dispersed metal particles.The computational study of the nickel binding energy has been conducted using density functional theory.It exhibits that the defects formed by heteroatom doping are beneficial to nickel anchoring and deposition to form highly uniform nickel particles.The phosphorus species in combination with the defects are suitable for H_(2) adsorption and dissociation.These results reveal that the heteroatomic doping on the active carbon shows significant effects in the hydrogenation of the liquid-phase aromatic compounds.These findings could provide a promising route for the rational design of aromatic compound hydrogenation catalysts to significantly decrease the cost by instead using noble metal catalysts in the industry.展开更多
The design and development of energy storage device with high energy/power density has become a research hotspot.Zinc-ion hybrid capacitors(ZHCs)are considered as one of the most promising candidates.However,the appli...The design and development of energy storage device with high energy/power density has become a research hotspot.Zinc-ion hybrid capacitors(ZHCs)are considered as one of the most promising candidates.However,the application of ZHCs is hindered by their low energy density at high power density due to the unsatisfactory cathode material.In this study,a novel 3D phosphorus-doped carbon nanotube/reduced graphene oxide(P-CNT/rGO)aerogel cathode is synthesized through a synergistic modification strategy of CNT insertion and P doping modification combined with 3D porous design.The as-obtained P-CNT/rGO aerogel cathode manifests significantly increased surface aera,expanded interlayer spacing,and enhanced pseudocapacitance behavior,thus leading to significantly enhanced specific capacitance and superb ions transport performance.The as-assembled ZHC based on P-CNT/rGO cathode delivers a superior energy density of 42.2 Wh/kg at an extreme-high power density of 80 kW/kg and excellent cycle life.In-depth kinetic analyses are undertaken to prove the enhanced pseudocapacitance behavior and exceptional power output capability of ZHCs.Furthermore,the reaction mechanism of physical and chemical adsorption/desorption of electrolyte ions on the P-CNT/rGO cathode is revealed by systematic ex-situ characterizations.This work can provide a valuable reference for developing advanced graphene-based cathode for high energy/power density ZHCs.展开更多
基金supported by the Petrochemical Research Institute Foundation(21-CB-09-01)the National Natural Science Foundation of China(22302186,22025205)+1 种基金the China Postdoctoral Science Foundation(2022M713030,2023T160618)the Fundamental Research Funds for the Central Universities(WK2060000058,WK2060000038).
文摘By simplifying catalyst-product separation and reducing phosphorus waste,heterogeneous hydroformylation offers a more sustainable alternative to homogeneous processes.However,heterogeneous hydroformylation catalysts developed thus far still suffer from the issues of much lower activity and metal leaching,which severely hinder their practical application.Here,we demonstrate that incorporating phosphorus(P)atoms into graphitic carbon nitride(PCN)supports facilitates charge transfer from Rh to the PCN support,thus largely enhancing electronic metal-support interactions(EMSIs).In the styrene hydroformylation reaction,the activity of Rh_(1)/PCN single-atom catalysts(SACs)with varying P contents exhibited a volcano-shaped relationship with P doping,where the Rh_(1)/PCN SAC with optimal P doping showed exceptional activity,approximately 5.8-and 3.3-fold greater than that of the Rh_(1)/g-C_(3)N_(4)SAC without P doping and the industrial homogeneous catalyst HRh(CO)(PPh_(3))_(3),respectively.In addition,the optimal Rh_(1)/PCN SAC catalyst also demonstrated largely enhanced multicycle stability without any visible metal aggregation owing to the increased EMSIs,which sharply differed from the severe metal aggregation of large nanoparticles on the Rh_(1)/g-C_(3)N_(4)SAC.Mechan-istic studies revealed that the enhanced catalytic performance could be attributed to electron-deficient Rh species,which reduced CO adsorption while simultaneously promoting alkene adsorption through increased EMSIs.These findings suggest that tuning EMSIs is an effective way to achieve SACs with high activity and durability.
基金supported by National Science Foundation of Shandong Province(Nos.ZR2023ME155 and ZR2023ME085)the Taishan Scholar Project of Shandong Province(Nos.tsqn202306226 and tsqn202211171).
文摘The development of high-performance lithium-ion batteries(LIBs)hinges on searching for advanced anode materials with large specific capacities as well as high cycling stability.However,traditional graphite anodes have not met the demand for higher energy storage owing to the deficiency of low lithium storage capacity.In the current work,we focus on designing one composite anode material with multiscale porous(MP)structure and phosphorus(P)doping.The coupling effects of three-dimensional(3D)interconnected skeleton,hollow pore channels,and P doping can facilitate the electrolyte diffusion and the mass transfer,as well as accommodate the volume changes during lithiation/delithiation processes.As expected,the as-prepared MP-SiGeSnSbPAl composite exhibits superior lithium storage performance,achieving a specific capacity of 827.9 mAh/g after 150 cycles at 200 mA/g and maintaining the high capacity of 456.7 mAh/g after 400 cycles at 1 A/g.Contrastively,the corresponding surplus capacities are only 590.3 and 225.7 mAh/g for the non-doped counterparts,respectively.In particular,MP-SiGeSnSbPAl displays much more stable cycling performances under the measurement of high areal mass loading of~3 mg/cm^(2)and the full-cell tests with the lithium iron phosphate as the cathode.This work witnesses one scalable protocol for preparing multinary Si-based composite in terms of facile operation and high lithium storage performances.
文摘Hydrogenated silicon carbide films (SiC:H) were deposited using the electron cyclotron resonance chemical vapour deposition (ECR-CVD) technique from a mixture of methane, silane and hydrogen, and using diborane and phosphine as doping gases. The effects of changes in the microwave power on the deposition rate and optical bandgap were investigated, and variations in the photoand dark-conductivities and activation energy were studied in conjunction with film analysis using the Raman scattering technique. In the case of boron-doped samples, the conductivity increased rapidly to a maximum, followed by rapid reduction at high microwave power. The ratio of the photo- to dark-conductivity (σph/σd) peaked at microwave power of ~600 W. Under conditions of high microwave power, Raman scattering analysis showed evidence of the formation and increase in the silicon microcrystalline and diamond-like phases in the films, the former of which could account for the rapid increase and the latter the subsequent decrease in the conductivity.In the case of phosphorusdoped SiC:H samples, it was found that increase in the microwave power has the effect of enhancing the formation of the silicon microcrystalline phase in the films which occurred in correspondence to a rapid increase in the conductivity and reduction in the activation energy The conductivity increase stabilised in samples deposited at microwave power exceeding 500 W probably as a result of dopant saturation. Results from Raman scattering measurements also showed that phosphorus doping had the effect of enhancing the formation of the silicon microcrystals in the film whereas the presence of boron had the effect of preserving the amorphous structure.
文摘Correction to:Rare Met.https://doi.org/10.1007/s12598-021-01864-4 In the original publication,the affiliation of the 5th author(Corresponding author)was published incorrectly.The correct affiliation is given in this Correction.The original publication has been corrected.
基金the National Natural Science Foundation of China(Nos.91961126 and 22078029)Zhejiang Provincial Natural Science Foundation(No.LR21E020003)+1 种基金Postgraduate Research&Practice Innovation Program of Jiangsu Province(No.SJCX21_1180)Jiangsu Development&Reform Commission and Changzhou Development&Reform Commission for their support。
文摘Titanium dioxide is considered to be promising anode for sodium-ion batteries due to stable structure during the charge/discharge process.However,its practical application is hindered by the slow electron/ion transport.Herein,phosphorus-doped anatase TiO_(2) nanoparticles with oxygen vacancies are successfully synthesized and utilized as high-performance sodium-storage materials.The dual strategy of phosphorus-doping and oxygen vacancies can concurrently boost electronic conductivity and adjust ion diffusion kinetics.They significantly contribute to the improved rate performance(167 mAh·g^(-1) at 20.0C)and stable cycling(95.9%after 2000 cycles at 20.0C).The proposed dual strategy can be potentially used to improve other oxide anodes for rechargeable batteries.
基金supported by the National Natural Science Foundation of China (22065015)Key Research Program of Jiangxi Province of China (20202BBEL53023)the Natural Science Foundation of Jiangxi Province (Grant Nos. 20212BAB203015 and 20212BCJL23053)。
文摘The electrolysis of water into hydrogen and oxygen provides an effective means of storing electrical energy indirectly.The current challenge is to design an optimal catalyst that exhibits low overpotentials,long-term stability,universal availability,and only uses inexpensive materials.Herein,a Co3O4nanoflower/stainless steel(P-Ov-CO_(3)O_(4)/SS) catalyst with both oxygen vacancies(Ovs) and phosphorus doping was perfectly prepared via a simple three-step method.The Ovs promoted charge transfer and accelerated the electrocatalysis,while P finely tuned the surface charge state.This resulted in numerous active sites for catalysis,and the synergistic effect of phosphorus doping and oxygen vacancies was finely demonstrated.The resultant electrocatalyst exhibited low hydrogen evolution overpotentials of 118 mV(-10 mA·cm^(-2)) and 242(-200 mA·cm^(-2)),as well as oxygen evolution overpotentials of 327 mV(100 mA·cm^(-2)) and 370 mV(200 mA·cm^(-2)),owing to the excellent synergistic effect of the Ovs and low-temperature phosphating.Moreover,P-Ov-Co_(3)O_(4)/SS//P-Ov-Co_(3)O_(4)/SS exhibited a low water splitting voltage of 1.681 V at 20 mA.cm-2.These findings will enable the synthesis of novel high-performance electrocatalysts for overall water splitting.
基金supported by the Guangdong Provincial Science and Technology Project of China (2011B010400016)China Postdoctoral Science Foundation (No. 20110490878)
文摘Phosphorus-doped carbon nanospheres without any metal residues were synthesized and characterized. The results revealed that the doping phosphorus atoms could significantly improve the electrocatalytic activity of graphitic carbon for the oxygen-reduction reaction （ORR） both in acidic and alkaline media, and the materials exhibited high electrocatalytic activity, long-term stability, and excellent tolerance to crossover effects especially in alkaline media. Quantum mechanics calculations with the density functional theory demonstrated that the changes in charge density and energetic characteristics of frontier orbitals for the P-doped graphene sheet could facilitate the ORR.
基金supported by grants from the National Research Foundation of Korea(NRF-2020R1A2C2008798)Korea University。
文摘Compact supercapacitors(SCs)have attracted attention for their great potential to replace bulky aluminum electrolytic capacitors(AECs)in alternating current(AC)line filtering applications.Herein,the fabrication of a high-frequency SC is reported using Ketjen black(KB)nanoparticles doped with phosphorus(P)to achieve a high areal capacitance of up to 2.26 mF cm^(-2)along with a high-rate capability,with a phase angle of-80.2°at 120 Hz.The high performance of the phosphorus-doped KB(designated PKB)SC with a 6 M KOH aqueous electrolyte is associated with its increased surface wettability and additional capacitive sites provided by the P-doping.Density functional theory(DFT)calculations further indicate that the P-doping enhances the interactions between the electrolyte ions and the carbon surface,thus leading to an improved electrochemical performance.These results suggest that the P-doped carbonbased SC could be highly favored in replacing conventional AECs in various high-frequency electronic devices.
基金supported by the National Natural Science Foundation of China(No.52273274)State Key Laboratory of Organic-Inorganic Composites(No.oic-202101010)Natural Science Basic Research Project of Shaanxi Province(No.2022JQ-123).
文摘Phosphorus-doped mesoporous carbons(PMCs)were prepared using a self-doping and self-templating approach via direct pyrolysis of sodium phytate(C_(6)H_(17)NaO_(24)P_(6)).The one-pot method allows simultaneous carbonization and P doping,eliminating the need for pre-synthesis or post-activation treatment.The C_(6)H_(17)NaO_(24)P_(6)is the source of both carbon and phosphorus,and the nano-Na_(4)P_(2)O_(7)particles produced during pyrolysis act as hard templates for the honeycomb mesoporous structure with high specific surface area(884–827m^(2)/g),large mesopore volume ratio(67%–75%)and rich phosphorus content(0.53–2.34 at%).As electrodes of supercapacitors in 6 mol/L KOH,the PMCs showed outstanding performance with a high capacitance of 202 F/g and excellent rate performance of 148 F/g at 30 A/g.In addition,the PMCs-based symmetrical supercapacitors can operate in an expanded working voltage of 0–1.6 V in 3mol/L H_(2)SO_(4)aqueous electrolytes with high-density energy of 11.8 Wh/kg.
基金This work was supported by the National Natural Science Foundation of China(U1564205)the Project of Construction of Innovative Teams and Teacher Career Development for Universities and Colleges under the Beijing Municipality(IDHT20180508).Naser Tavajohi acknowledges financial support from the Kempe Foundation.
文摘Owing to their high theoretical specific capacity and low cost, lithium- and manganese-rich layered oxide (LMR) cathode materials are receiving increasing attention for application in lithium-ion batteries. However, poor lithium ion and electron transport kinetics plus side effects of anion and cation redox reactions hamper power performance and stability of the LMRs. In this study, LMR Li_(1.2)Mn_(0.6)Ni_(0.2)O_(2) was modified by phosphorus (P)-doping to increase Li+ conductivity in the bulk material. This was achieved by increasing the interlayer spacing of the lithium layer, electron transport and structural stability, resulting in improvement of the rate and safety performance. P^(5+) doping increased the distance between the (003) crystal planes from ~0.474 nm to 0.488 nm and enhanced the structural stability by forming strong covalent bonds with oxygen atoms, resulting in an improved rate performance (capacity retention from 38% to 50% at 0.05 C to 5 C) and thermal stability (50% heat release compared with pristine material). First-principles calculations showed the P-doping makes the transfer of excited electrons from the valence band to conduction band easier and P can form a strong covalent bond helping to stabilize material structure. Furthermore, the solid-state electrolyte modified P5+ doped LMR showed an improved cycle performance for up to 200 cycles with capacity retention of 90.5% and enhanced initial coulombic efficiency from 68.5% (pristine) or 81.7% (P-doped LMR) to 88.7%.
基金supported by the National Key Research and Development Program of China(2018YFA0305900 and 2023YFA1406200)。
文摘Diamond is known as the ultimate semiconductor owing to its excellent physical properties.However,the high difficulty of n-type doping and the poor electrical performance of n-type diamonds remain major challenges for the application of diamond semiconductor materials.In this paper,a high-pressure thermal diffusion method for the n-type doping of diamond,which utilizes high pressure to reduce the volume difference between phosphorus atoms and carbon atoms,is reported for the first time.This method can achieve efficient doping and ionization of phosphorus atoms at the lattice sites of diamond.The prepared phosphorus-doped diamond exhibited the lowest resistivity(2Ωcm)and highest electron concentration(2.27×10^(18) cm^(-3))observed in any known phosphorus-doped diamond single crystal at room temperature(300 K).The high-pressure thermal diffusion method provides an effective approach for diamond n-type doping,which may play an important role in the design and preparation of future diamond-based semiconductor devices.
基金supported by the National Natural Science Foundation of China(No.21575115)the Program for Chang Jiang Scholars and Innovative Research Team,Ministry of Education,China(No.IRT-16R61)。
文摘Hematite(α-Fe_(2)O_(3))is a promising photoanode for photoelectrochemical(PEC)water splitting.However,the severe charge recombination and sluggish water oxidation kinetics extremely limit its use in photohydrogen conversion.Herein,a co-activation strategy is proposed,namely through phosphorus(P)doping and the loading of CoAl-layered double hydroxides(CoAl-LDHs)cocatalysts.Unexpectedly,the integrated system,CoAl-LDHs/P-Fe_(2)O_(3) photoanode,exhibits an outstanding photocurrent density of 1.56 mA/cm^(2) at 1.23 V(vs.reversible hydrogen electrode,RHE),under AM 1.5 G,which is 2.6 times of pureα-Fe_(2)O_(3).Systematic studies reveal that the remarkable PEC performance is attributed to accelerated surface OER kinetics and enhanced carrier separation efficiency.This work provides a feasible strategy to enhance the PEC performance of hematite photoanodes.
基金supported by the National Natural Science Foundation of China(NSFC,grant nos.22122202 and 22072051)Zhenjiang Key Research and Development Program,Industry Foresight and Common Key Technologies,China(grant no.CQ2022006).
文摘The inadequate performance of oxygen reduction reaction(ORR)catalysts hampers the development of proton exchange membrane fuel cells(PEMFCs).Herein,we proposed an approach to tackle this problem by modulating the chemical bond type of intermetallic Pt-based catalysts,using phosphorus(P)doped L1_(0)-PtFeGa_(0.1)/C(P-L1_(0)-PtFeGa_(0.1)/C)as a proof of concept.X-ray absorption spectroscopy(XAS)demonstrated that the doped P transferred electrons to Pt,and thus,modified the electronic structure of Pt,weakening the adsorption strength with oxygen-containing species.Therefore P-L1_(0)-PtFeGa_(0.1)/C showed 13 times mass activity(MA)compared with commercial Pt/C,with a decay of only 28%after 100,000 potential cycles.When equipped in the membrane electrode assembly,the P-L1_(0)-PtFeGa_(0.1)/C catalyst also exhibited a remarkable activity(MA=0.84 A mgPt^(−1)at 0.9 V)and stability(MA retention=72%and voltage loss=9 mVat 0.8 A cm^(−2)after 30,000 cycles),making it one of the best performers among recorded Pt-based catalysts.Theoretical studies demonstrated that the doping of P optimized the adsorption energy between Pt and oxygen intermediates through sp-d orbital interactions and prevented metal dissolution by forming stronger Pt-P covalent bonds compared with Pt–Pt bonds.
文摘P‐doped TiO2 (PTIO) thin‐films with different P contents were prepared using a sol‐gel method. The thin‐film samples were characterized using various techniques. The photocatalytic activity was evaluated by decomposing butyl benzyl phthalate under visible‐light irradiation. The results showed that the transformation of anatase to the rutile phase was inhibited and grain growth of TiO2 was prevented by P doping. The results confirm that the doped P atoms existed in two chemical forms, and those incorporated in the TiO2 lattice may play a positive role in photocatalysis. The high photocatalytic activities of the PTIO thin‐films may be the result of extrinsic absorption through the creation of oxygen vacancies, rather than excitation of the intrinsic absorption band of bulk TiO2 . The PTIO can be recycled with little depression of the photocatalytic activity. After six cycles, the photocatalytic activity of the PTIO film was still higher than 98%.
基金supported by the National Natural Science Foundation of China(52072196)the Major Basic Research Program of the Natural Science Foundation of Shandong Province(ZR2020ZD09)。
文摘MoS_(2)is a promising electrocatalyst because of its natural abundance and outstanding electrochemical stability.However,the poor conductivity and low activity limit its catalytic performance;furthermore,MoS_(2)is unable to satisfy the requirements of most industrial applications.In this study,to obtain a P-doped MoS_(2)catalyst with S vacancy defects,P is inserted into the MoS_(2)matrix via a solid phase ion exchange at room temperature.The optimal P-doping amount is 11.4 wt%,and the resultant catalyst delivers excellent electrocatalytic properties for the hydrogen evolution reaction(HER)and oxygen evolution reaction(OER)with the corresponding overpotentials of 93 and 316 mV at 10 mA cm^(-2) in an alkaline solution;these values surpass the overpotentials of most previously reported MoS_(2)-based materials.Theoretical calculations and results demonstrate that the synergistic effect of the doped P,which forms active centers in the basal plane of MoS_(2),and S vacancy defects caused by P doping intensifies the intrinsic electronic conductivity and electrocatalytic activity of the catalyst.Density functional theory calculations demonstrate that P optimizes the free energy of the MoS_(2)matrix for hydrogen adsorption,thereby considerably increasing the intrinsic activity of the doped catalyst for the HER compared with that observed from pristine MoS_(2).The enhanced catalytic activity of P-doped MoS_(2)for the OER is attributed to the ability of the doped P which facilitates the adsorption of hydroxyl and hydroperoxy intermediates and reduces the reaction energy barrier.This study provides a new environmentally friendly and convenient solid-phase ion exchange method to improve the electrocatalytic capability of two-dimensional transition-metal dichalcogenides in largescale applications.
基金supported by the National Natural Science Foundation of China(Nos.21878195 and U20A20145)the Scientific and technological achievement transformation project of Sichuan Science and Technology Department(No.21ZHSF0111)Shanghai Scientific and Technological Innovation Project(No.18JC1410604).
文摘Heteroatom doping is one of the most promising strategies toward regulating intrinsically sluggish electronic conductivity and kinetic reaction of transition metal oxides for enhancing their lithium storage.Herein,we designed phosphorus-doped NiMo0_(4) nanorods(P-NiMo0_(4))by using a facile hydrothermal method and subsequent low-temperature phosphorization treatment.Phosphorus doping played an indispensable role in significantly improving electronic conductivity and the Li+diffusion kinetics of NiMo0_(4) materials.Experimental investigation and density functional theory calculation demonstrated that phosphorus doping can expand the interplanar spacing and alter electronic structures of NiMo0_(4) nanorods.Meanwhile,the introduced phosphorus dopant can generate some oxygen vacancies on the surface of NiMo0_(4),which can accelerate Li+diffusion kinetics and provide more active site for lithium storage.As excepted,P-NiMo0_(4) electrode delivered a high specific capacity(1,130 mA·g^(-1) at 100 mA·g^(-1) after 100 cycles),outstanding cycling durability(945 mA·g^(-1) at 500 mA·g^(-1) over 200 cycles),and impressive rate performance(640 mA·g^(-1)at 2,000mA·g^(-1))for lithium ion batteries(LIBs).This work could provide a potential strategy for improving intrinsic conductivity of transition metal oxides as high-performance anodes for LIBs.
基金supported by the Henan Province Education Department Natural Science Research Item(No.21A480005)the Research Project at School-level of Henan University of Technology(No.2020BS017).
文摘The controllable construction of non-noble metal based bifunctional catalysts with high activities towards oxygen reduction reaction(ORR)and oxygen evolution reaction(OER)is of great significance,but remains a challenge.Herein,we reported an effective method to synthesize cobalt-nitrogen doped mesoporous carbon-based bifunctional oxygen electrocatalyst with controllable phosphorus content(Co-N-P_(X)-MC,X=0.5,1.0,1.5,2.0).The mesoporous carbon substrate endowed the asprepared samples with more exposed active surface(236.50 m^(2)·g^(−1))and the most appropriate doping ratio of phosphorus had been investigated to be 1.5(Co-N-P1.5-MC).For ORR,Co-N-P1.5-MC exhibited excellent catalytic activity with more positive onset potential(1.01 V)and half-wave potential(0.84 V)than the other samples.For OER,Co-N-P1.5-MC also showed a low overpotential of 415 mV.Combining experimental results and density-functional theory(DFT)calculations,the outstanding bifunctional catalytic performance of Co-N-P1.5-MC was due to the synergistic cooperation between the P and N dopants,which could reduce the reaction barriers and was favorable for ORR and OER.Moreover,the Zn-air battery using Co-N-P1.5-MC as the cathode showed remarkable battery performance with high stability(could operate stably for over 160 h at 10 mA·cm^(−2))and maximum power density(119 mW·cm^(−2)),demonstrating its potential for practical applications.This work could provide significant enlightenment towards the design and construction of bifunctional oxygen electrocatalyst for next-generation electrochemical devices.
基金This work was supported by the National Natural Science Foundation of China(Grant No.21908185)Project of Hunan Provincial Natural Science Foundation of China(Grant No.2018JJ3497)+1 种基金Project of Hunan Provincial Education Department(Grant Nos.19B572 and 20B547)Collaborative Innovation Center of New Chemical Technologies for Environmental Benignity and Efficient Resource Utilization,and National Department of Education Engineering Research Centre for Chemical Process Simulation and Optimization.
文摘This work proposes a modified activated carbon support,with defects and heteroatoms(N,P-ACs)by nitrogen and phosphorus doping to load non-noble nickel to catalyze aromatic compound hydrogenation.The Ni/N,P-ACs-900(prepared at 900℃)showed promising catalytic activity in liquid-phase 1,5-dinitronaphthalene hydrogenation with a 1,5-diaminonaphthalene yield of 95.8% under the mild condition of 100℃,which is comparable to the commercial Pd/C catalyst.The nitrogen species were burned off at 900℃,causing more defects for nickel metal loading,facilitating the interaction between the supports and the nickel metal,and resulting in highly dispersed metal particles.The computational study of the nickel binding energy has been conducted using density functional theory.It exhibits that the defects formed by heteroatom doping are beneficial to nickel anchoring and deposition to form highly uniform nickel particles.The phosphorus species in combination with the defects are suitable for H_(2) adsorption and dissociation.These results reveal that the heteroatomic doping on the active carbon shows significant effects in the hydrogenation of the liquid-phase aromatic compounds.These findings could provide a promising route for the rational design of aromatic compound hydrogenation catalysts to significantly decrease the cost by instead using noble metal catalysts in the industry.
基金financially supported by Distinguished Young Scientists of Hunan Province(No.2022JJ10024)National Natural Science Foundation of China(No.21601057)+1 种基金Natural Science Foundation of Hunan Province(No.2021JJ30216)Key Projects of Hunan Provincial Education Department(No.22A0412).
文摘The design and development of energy storage device with high energy/power density has become a research hotspot.Zinc-ion hybrid capacitors(ZHCs)are considered as one of the most promising candidates.However,the application of ZHCs is hindered by their low energy density at high power density due to the unsatisfactory cathode material.In this study,a novel 3D phosphorus-doped carbon nanotube/reduced graphene oxide(P-CNT/rGO)aerogel cathode is synthesized through a synergistic modification strategy of CNT insertion and P doping modification combined with 3D porous design.The as-obtained P-CNT/rGO aerogel cathode manifests significantly increased surface aera,expanded interlayer spacing,and enhanced pseudocapacitance behavior,thus leading to significantly enhanced specific capacitance and superb ions transport performance.The as-assembled ZHC based on P-CNT/rGO cathode delivers a superior energy density of 42.2 Wh/kg at an extreme-high power density of 80 kW/kg and excellent cycle life.In-depth kinetic analyses are undertaken to prove the enhanced pseudocapacitance behavior and exceptional power output capability of ZHCs.Furthermore,the reaction mechanism of physical and chemical adsorption/desorption of electrolyte ions on the P-CNT/rGO cathode is revealed by systematic ex-situ characterizations.This work can provide a valuable reference for developing advanced graphene-based cathode for high energy/power density ZHCs.
基金supported by the National Natural Science Foundation of China(61404116,11975212)Guangdong Basic and Applied Basic Research Foundation(2023A1515010073)the Scientific Research Foundation for the Returned Overseas Chinese Scholars(KZ15Z20053)。
