Density functional theory(DFT)calculations were employed to investigate the adsorption behavior of NH_(3),AsH_(3),PH_(3),CO_(2),and CH_(4)molecules on both pristine and mono-vacancy phosphorene sheets.The pristine pho...Density functional theory(DFT)calculations were employed to investigate the adsorption behavior of NH_(3),AsH_(3),PH_(3),CO_(2),and CH_(4)molecules on both pristine and mono-vacancy phosphorene sheets.The pristine phosphorene surface showsweak physisorption with all the gasmolecules,inducing onlyminor changes in its structural and electronic properties.However,the introduction ofmono-vacancies significantly enhances the interaction strength with NH_(3),PH_(3),CO_(2),and CH_(4).These variations are attributed to substantial charge redistribution and orbital hybridization in the presence of defects.The defective phosphorene sheet also exhibits enhanced adsorption energies,along with favorable sensitivity and recovery characteristics,highlighting its potential as a promising gas sensor for NH_(3),AsH_(3),PH_(3),CO_(2),and CH_(4)at ambient conditions.展开更多
In two-dimensional bilayer systems,twist-angle-dependent electronic and thermoelectric properties have garnered significant scientific interest in recent years.In this work,based on a combination of density functional...In two-dimensional bilayer systems,twist-angle-dependent electronic and thermoelectric properties have garnered significant scientific interest in recent years.In this work,based on a combination of density functional theory and nonequilibrium Green’s function method,we explore the electronic and thermoelectric properties in blue-phosphorene nanoribbon-based heterojunction(BPNRHJ)with and without blue-phosphorene nanoribbon(BPNR)stack.Our calculations find that the electronic conductance and power factor can be strongly enhanced by the BPNR stack,and their enhancements can be further observed with the twist between the layers.The main reason for this is the electronic hybridization between the layers can provide new transport channels,and the twist can modulate the strength of interlayer electronic hybridization,resulting in extremely violent fluctuations in electron transmission and hence an enhanced power factor.While the phonon thermal conductance exhibits very low dependence on the layer stack and twist.Combining these factors,our results reveal that the thermoelectric performance can be greatly modulated and enhanced in twist bilayer BPNRHJ:the figure of merit will be over 2.5 in 4-4-ZBPNR@ZGNR-AA-8.8∘at 500 K.展开更多
The electrochemical ammonia synthesis has attracted increasing attention due to its energy saving characteristics.However,developing novel electrocatalysts and their mechanism remain great challenges.Here,several tran...The electrochemical ammonia synthesis has attracted increasing attention due to its energy saving characteristics.However,developing novel electrocatalysts and their mechanism remain great challenges.Here,several transition metal(TM)atoms doped on phosphorene were studied as N2 fixation electrocatalysts by using density functional theory(DFT)calculations.The results demonstrate that single Ru atom doped phosphorene shows an excellent catalytic activity for ammonia synthesis via the enzymatic pattern.A small overpotential of 0.696 V is achieved for this process.The effect of oxidation in the catalyst was also discussed in our work.Oxidation deactivates the catalyst,which should be avoided in the experiment.Our outcomes offer a novel perspective for single-atom catalytic ammonia synthesis with phosphorene as a substrate.展开更多
Semiconductor photocatalysis is a potential pathway to solve the problems of global energy shortage and environmental pollution.Black phosphorus(BP)has been widely used in the field of photocatalysis owing to its feat...Semiconductor photocatalysis is a potential pathway to solve the problems of global energy shortage and environmental pollution.Black phosphorus(BP)has been widely used in the field of photocatalysis owing to its features of high hole mobility,adjustable bandgap,and wide optical absorption range.Nevertheless,pristine BP still exhibits unsatisfactory photocatalytic activity due to the low separation efficiency of photoinduced charge carriers.In recent years,the construction of heterostructured photocatalysts based on BP has become a research hotspot in photocatalysis with the remarkable improvement of photoexcited charge-separation efficiency.Herein,progress on the design,synthesis,properties,and applications of BP and its corresponding heterostructured photocatalysts is summarized.Furthermore,the photocatalytic applications of BP-based heterostructured photocatalysts in water splitting,pollutant degradation,carbon dioxide reduction,nitrogen fixation,bacterial disinfection,and organic synthesis are reviewed.Opportunities and challenges for the exploration of advanced BP-based heterostructured photocatalysts are presented.This review will promote the development and applications of BP-based heterostructured photocatalysts in energy conversion and environmental remediation.展开更多
First-principles calculations based on van der Waals(vdW) corrected density functional theory(DFT) are firstly employed to investigate the adsorption of methanol(CH_3OH) gas molecule on pristine and Xdoped phosphorene...First-principles calculations based on van der Waals(vdW) corrected density functional theory(DFT) are firstly employed to investigate the adsorption of methanol(CH_3OH) gas molecule on pristine and Xdoped phosphorene( =B, C, N and O). The CH_3OH gas molecule is placed on the top of different phosphorene surfaces, the whole adsorption systems are fully optimized by using Vienna ab initio simulation package(VASP). The calculation results demonstrate that both pristine and heteroatomdoped phosphorene are sensitive to CH_3OH gas molecule with a moderate adsorption energy and an excellent charge transfer. Among all the investigated adsorption configurations, CH_3OH gas molecule is physically absorbed on pristine phosphorene and heteroatom-doped phosphorene. The N and O doping improve the adsorption of phosphorene with CH_3OH gas molecule, while B and C doping are almost not beneficial compared to the pristine phosphorene. The results suggest that N-doped and O-doped phosphorene are ideal candidates used for CH_3OH gas sensing.展开更多
We investigate the electronic and transport properties of one-dimensional armchair phosphorene nanoribbons(APNRs) containing atomic vacancies with different distributions and concentrations using ab initio density fun...We investigate the electronic and transport properties of one-dimensional armchair phosphorene nanoribbons(APNRs) containing atomic vacancies with different distributions and concentrations using ab initio density functional calculations. It is found that the atomic vacancies are easier to form and detain at the edge region rather than a random distribution through analyzing formation energy and diffusion barrier. The highly local defect states are generated at the vicinity of the Fermi level, and emerge a deep-to-shallow transformation as the width increases after introducing vacancies in APNRs.Moreover, the electrical transport of APNRs with vacancies is enhanced compared to that of the perfect counterparts. Our results provide a theoretical guidance for the further research and applications of PNRs through defect engineering.展开更多
According to first-principles calculations, it is our prediction that bilayer phosphorene（BLP） will become a quasitwo-dimensional superconductor under a certain degree of interlayer compression. A decreasing interla...According to first-principles calculations, it is our prediction that bilayer phosphorene（BLP） will become a quasitwo-dimensional superconductor under a certain degree of interlayer compression. A decreasing interlayer distance may realize the transition in the BLP from a semiconducting phase to a metallic phase. On the other hand, a severe vertical compression may make the BLP lattice become dynamically unstable. It is found that in the stable metallic phase of the BLP, interlayer phonon modes dominate the electron-phonon coupling λ. The obtained λ can be greater than 1 and the superconducting temperature T_c can be higher than 10 K.展开更多
As a clean and renewable future energy source, hydrogen fuel can be produced via solar water splitting. Two-dimensional (2D) black phosphorene (black-P) can harvest visible light due to the desirable band gap, which p...As a clean and renewable future energy source, hydrogen fuel can be produced via solar water splitting. Two-dimensional (2D) black phosphorene (black-P) can harvest visible light due to the desirable band gap, which promises it as a metal-free photocatalyst. However, black-P can be only used to produce hydrogen since the oxidation potential of water locates lower than the position of the valence band maximum. To improve the photocatalytic performance of black-P, here, using black-P and blue phosphorene (blue-P) monolayers, we propose a 2D van der Waals (vdW) heterojunction. Theoretical results, including the band structures, density of states, Bader charge population, charge density di erence, and optical absorption spectra, clearly reveal that the visible light absorption ability is obviously improved, and the band edge alignment of the proposed vdW heterojunction displays a typical type-II feature to effectively separate the photogenerated carriers. At the same time, the built-in interfacial electric field prevents the electron-hole recombination. These predictions suggest that the examined phosphorene-based vdW heterojunction is an efficient photocatalyst for solar water splitting.展开更多
Strain is a powerful tool to engineer the band structure of bilayer phosphorene.The band gap can be decreased by vertical tensile strain or in-plane compressive strain.At a critical strain,the gap is closed and the bi...Strain is a powerful tool to engineer the band structure of bilayer phosphorene.The band gap can be decreased by vertical tensile strain or in-plane compressive strain.At a critical strain,the gap is closed and the bilayer phosphorene is turn to be a semi-Dirac semimetal material.If the strain is stronger than the criterion,a band-inversion occurs and it re-happens when the strain is larger than another certain value.For the zigzag bilayer phosphorene ribbon,there are two edge band dispersions and each dispersion curve represents two degenerate edge bands.When the first band-inversion happens,one of the edge band dispersion disappears between the band-cross points while the other survives,and the latter will be eliminated between another pair of band-cross points of the second band-inversion.The optical absorption of bilayer phosphorene is highly polarized along armchair direction.When the strain is turn on,the optical absorption edge changes.The absorption rate for armchair polarized light is decreased by gap shrinking,while that for zigzag polarized light increases.The bandtouch and band-inversion respectively result in the sublinear and linear of absorption curve versus light frequency in low frequency limit.展开更多
We demonstrate theoretically the anisotropic quantum transport of electrons through an electric field on monolayer and multilayer phosphorene. Using the long-wavelength Hamiltonian with continuum approximation, we fin...We demonstrate theoretically the anisotropic quantum transport of electrons through an electric field on monolayer and multilayer phosphorene. Using the long-wavelength Hamiltonian with continuum approximation, we find that the transmission probability for transport through an electric field is an oscillating function of incident angle, electric field intensity, as well as the incident energy of electrons. By tuning the electric field intensity and incident angle, the channels can be transited from opaque to transparent. The conductance through the quantum waveguides depends sensitively on the transport direction because of the anisotropic effective mass, and the anisotropy of the conductance can be tuned by the electric field intensity and the number of layers. These behaviors provide us an efficient way to control the transport of phosphorene-based microstructures.展开更多
We demonstrate theoretically the anisotropic quantum transport of electrons through a single barrier on monolayer phosphorene. Using an effective k .p Hamiltonian, we find that the transmission probability for transpo...We demonstrate theoretically the anisotropic quantum transport of electrons through a single barrier on monolayer phosphorene. Using an effective k .p Hamiltonian, we find that the transmission probability for transport through n-n-n （or n p-n） junction is an oscillating function of the incident angle, the barrier height, as well as the incident energy of electrons. The conductance in such systems depends sensitively on the transport direction due to the anisotropic effective mass. By tuning the Fermi energy and gate voltage, the channels can be transited from opaque to transparent, which provides us with an efficient way to control the transport of monolayer phosphorene-based microstructures.展开更多
Searching alternatives to Pt-based catalyst for producing hydrogen via water splitting has gathered enormous attention to develop renewable energy. Phosphorene has been investigated widely for its large surface area, ...Searching alternatives to Pt-based catalyst for producing hydrogen via water splitting has gathered enormous attention to develop renewable energy. Phosphorene has been investigated widely for its large surface area, low cost, and high carrier mobility, however, the poor activity in hydrogen evolution reaction (HER) and low conductivity limit its practical application. Herein, on the basis of first-principles calculations, we demonstrate that the catalytic HER in phosphorene can be enhanced significantly with cobalt intercalations. The Co-intercalated phosphorene is metallic with charge transfer from Co atoms to phosphorene, which could enhance the catalytic activity of phosphorene. In addition, the calculated Gibbs free energy of hydrogen adsorption on Co-intercalated phosphorene bilayer is comparable to that on Pt(111) surface, independent of the degree of hydrogen coverage. Our study implies that the Co intercalation provides an effective approach to enhance the catalytic HER in phosphorene.展开更多
Black phosphorus with a superior theoretical capacity(2596 mAh g^(-1))and high conductivity is regarded as one of the powerful candidates for lithium-ion battery(LIB)anode materials,whereas the severe volume expansion...Black phosphorus with a superior theoretical capacity(2596 mAh g^(-1))and high conductivity is regarded as one of the powerful candidates for lithium-ion battery(LIB)anode materials,whereas the severe volume expansion and sluggish kinetics still impede its applications in LIBs.By contrast,the exfoliated two-dimensional phosphorene owns negligible volume variation,and its intrinsic piezoelectricity is considered to be beneficial to the Li-ion transfer kinetics,while its positive influence has not been discussed yet.Herein,a phosphorene/MXene heterostructure-textured nanopiezocomposite is proposed with even phosphorene distribution and enhanced piezo-electrochemical coupling as an applicable free-standing asymmetric membrane electrode beyond the skin effect for enhanced Li-ion storage.The experimental and simulation analysis reveals that the embedded phosphorene nanosheets not only provide abundant active sites for Li-ions,but also endow the nanocomposite with favorable piezoelectricity,thus promoting the Li-ion transfer kinetics by generating the piezoelectric field serving as an extra accelerator.By waltzing with the MXene framework,the optimized electrode exhibits enhanced kinetics and stability,achieving stable cycling performances for 1,000 cycles at 2 A g^(-1),and delivering a high reversible capacity of 524 m Ah g^(-1)at-20℃,indicating the positive influence of the structural merits of self-assembled nanopiezocomposites on promoting stability and kinetics.展开更多
Phosphorene is a two-dimensional semiconductor with layers-dependent bandgap in the near-infrared range and it has attracted a great deal of attention due to its high anisotropy and cartier mobility. The highly anisot...Phosphorene is a two-dimensional semiconductor with layers-dependent bandgap in the near-infrared range and it has attracted a great deal of attention due to its high anisotropy and cartier mobility. The highly anisotropic nature of phos- phorene has been demonstrated through Raman and polarization photoluminescence measurements. Photoluminescence spectroscopy has also revealed the layers-dependent bandgap of phosphorene. Furthermore, due to the reduced dimension- ality and screening in phosphorene, excitons and trions can stably exist at elevated temperatures and have large binding energies. The exciton and trion dynamics are thus detected by applying electrical bias or optical injection to the phospho- rene system. Finally, various optical and optoelectronic applications based on phosphorene have been demonstrated and discussed.展开更多
We have studied the structural and electronic properties of a hybrid hexagonal boron nitride with phosphorene nanocomposite using ab initio density functional calculations. It is found that the interaction between the...We have studied the structural and electronic properties of a hybrid hexagonal boron nitride with phosphorene nanocomposite using ab initio density functional calculations. It is found that the interaction between the hexagonal boron nitride and phosphorene is dominated by the weak van der Waals interaction, with their own intrinsic electronic properties preserved. Furthermore, the band gap of the nanocomposite is dependent on the interfacial distance. Our results could shed light on the design of new devices based on van der Waals heterostructure.展开更多
As an important anode material for fast-charging Li-ion batteries(LIBs),black phosphorus(BP)has attracted extensive attention.Black phosphorene nanotubes(BPNTs)can be theoretically produced by rolling up the black pho...As an important anode material for fast-charging Li-ion batteries(LIBs),black phosphorus(BP)has attracted extensive attention.Black phosphorene nanotubes(BPNTs)can be theoretically produced by rolling up the black phosphorene nanosheet along armchair(a-BPNTs)and zigzag(z-BPNTs)directions.The effects of curvature,chirality,Li-storage concentrations and strain stress on the Li-storage performance such as Li diffusion barriers and mechanical stabilities of BPNTs are mainly investigated by first principles calculations.The theoretical calculations predict that the a-BPNTs and z-BPNTs have good maximum Li-storage capacities,and the z-BPNTs exhibit better flexibility than a-BPNTs.The mechanical stabilities and Li-migration are all related to the curvature of BPNTs.Additionally,both a-BPNTs and z-BPNTs exhibit fast Li-ion conductivity along the c-axis direction.Moreover,the average Poisson's ratio of a-BPNTs(0.68)is larger than that of z-BPNTs(0.17),indicating that the strain stress is more difficult to apply on a-BPNTs than z-BPNTs.Our calculations predict that the a-BPNTs can afford ultrafast kinetic rate for fastcharging and high-power LIBs,while the z-BPNTs can provide extra capacity for high-energy LIBs.展开更多
Superior bifunctional electrocatalysts with ultra-high stability and excellent efficiency are crucial to boost the oxygen evolution reaction(OER) and the hydrogen evolution reduction(HER) in the overall water splittin...Superior bifunctional electrocatalysts with ultra-high stability and excellent efficiency are crucial to boost the oxygen evolution reaction(OER) and the hydrogen evolution reduction(HER) in the overall water splitting(OWS) for the sustainable production of clean fuels. Herein, comprehensive density functional theory(DFT) computations were performed to explore the potential of several single transition metal(TM) atoms anchored on various S-doped black phosphorenes(TM/Snx-BP) for bifunctional OWS electrocatalysis. The results revealed that these candidates display good stability, excellent electrical conductivity, and diverse spin moments. Furthermore, the Rh/S12-BP catalyst was identified as an eligible bifunctional catalyst for OWS process due to the low overpotentials for OER(0.43 V) and HER(0.02 V), in which Rh and its adjacent P atoms were identified as the active sites. Based on the computed Gibbs free energies of OH~*, O~*, OOH~* and H~*, the corresponding volcano plots for OER and HER were established.Interestingly, the spin moments and the charge distribution of the active sites determine the catalytic trends of OER and HER. Our findings not only propose a promising bifunctional catalyst for OWS, but also widen the potential application of BP in electrocatalysis.展开更多
We have investigated the electronic and magnetic properties of zigzag phosphorene nanoribbons(ZPNRs)with transition metal(TM)passivated atoms,it can be found that the ZPNRs with TM passivated atoms exhibit different m...We have investigated the electronic and magnetic properties of zigzag phosphorene nanoribbons(ZPNRs)with transition metal(TM)passivated atoms,it can be found that the ZPNRs with TM passivated atoms exhibit different magnetisms except for the Ni-passivated system.Meanwhile,the results show that the magnetic moments of ZPNRs with TM passivated atoms are larger than that of ZPNRs with other passivated non-metals/groups.Interestingly,it can be found that Fe-passivated ZPNR exhibits magnetic semiconducting character,which provides the possbility for the application of phosphorene in information storage.For Mn-passivated ZPNRs,it exhibits the half-metallicity.These results may be useful for potential applications of phosphorene in electronic and high-performance spintronic devices.展开更多
The synthesis of high-value multi-carbon products through the electrochemical reduction of carbon monoxide(COER) is one of the promising avenues for carbon utilization and energy storage,in which searching for efficie...The synthesis of high-value multi-carbon products through the electrochemical reduction of carbon monoxide(COER) is one of the promising avenues for carbon utilization and energy storage,in which searching for efficient electrocatalysts that exhibit moderate CO intermediate binding strength and low kinetic barrier for C-C coupling is a key issue.Herein,by means of comprehensive density functional theory(DFT) computations,we theoretically designed three synergistic coupling catalysts by co-doping transition metal(TM=Fe,Co and Ni) and boron(B) into the two-dimensional black phosphorene(BP),namely TMB@BP for COER to C_(2) products.DFT computations and ab initio molecular dynamics simulations reveal the good stability and high feasibility of these proposed TM-B@BP catalysts for practical applications and future experimental synthesis.More interestingly,high-value ethylene(C_(2)H_(4)),ethane(C_(2)H_(6)) and ethanol(C_(2)H_(5)OH) products can be obtained on these three designed electrocatalysts with ultra-small limiting potentials(-0.20~-0.41 V) and low kinetic energy barriers of C-C coupling(0.52~0.91 eV).Meanwhile,the competitive one-carbon(C_(1)) products and hydrogen evolution reaction can also be effectively suppressed.The promising activity and selectivity of these three designed electrocatalysts render them ideal candidates for CO electroreduction,thus providing a cost-effective opportunity to achieve a sustainable production of high value C_(2) chemicals and fuels.展开更多
There is an ideal desire to develop the high-performance anodes materials for Liion batteries(LIBs),which requires not onlyhigh stability and reversibility,but also rapidcharging/discharging rate.In this work,webuilta...There is an ideal desire to develop the high-performance anodes materials for Liion batteries(LIBs),which requires not onlyhigh stability and reversibility,but also rapidcharging/discharging rate.In this work,webuiltablue phosphorene-graphene(BlueP-G)intralayer heterostructure by connecting BlueP and graphene monolayers at zigzag edges with covalent bonds.Based on the density functional theory simulation,the electronic structure of the heterostructure,Li adsorption and Li diffusion on heterostructure were systematically investigated.Compared with the pristine BlueP,the existence of graphene layer increases the overall conductivity of BlueP-G intralayer heterostructure.The significantly enhanced adsorption energy indicates the Li deposition on anode surface is energetically favored.The fast diffusion of Li with energy barrier as low as 0.02-0.09 eV indicates the growth of Li dendrite could be suppressed and the stability and reversibility of the battery will be increased.With a combination of increased conductivity of electronic charge,excellent Li adsorption and Li mobility on surface,BlueP-G intralayer heterostructure with zigzag interface is quite promising in the application of anode material for Li-ion batteries.展开更多
基金financial support to conduct this research from the Science and Engineering Research Board(SERB)through a state university research excellence(SURE)grant(SUR/2022/004935).
文摘Density functional theory(DFT)calculations were employed to investigate the adsorption behavior of NH_(3),AsH_(3),PH_(3),CO_(2),and CH_(4)molecules on both pristine and mono-vacancy phosphorene sheets.The pristine phosphorene surface showsweak physisorption with all the gasmolecules,inducing onlyminor changes in its structural and electronic properties.However,the introduction ofmono-vacancies significantly enhances the interaction strength with NH_(3),PH_(3),CO_(2),and CH_(4).These variations are attributed to substantial charge redistribution and orbital hybridization in the presence of defects.The defective phosphorene sheet also exhibits enhanced adsorption energies,along with favorable sensitivity and recovery characteristics,highlighting its potential as a promising gas sensor for NH_(3),AsH_(3),PH_(3),CO_(2),and CH_(4)at ambient conditions.
基金supported by the Key Projects of Department of Education of Hunan Province,China(Grant No.21A0167)the Natural Science Foundation of Hunan Province,China(Grant No.2019JJ40532)the Talent Introducing Foundation of Central South University of Forestry and Technology(Grant No.104-0160)。
文摘In two-dimensional bilayer systems,twist-angle-dependent electronic and thermoelectric properties have garnered significant scientific interest in recent years.In this work,based on a combination of density functional theory and nonequilibrium Green’s function method,we explore the electronic and thermoelectric properties in blue-phosphorene nanoribbon-based heterojunction(BPNRHJ)with and without blue-phosphorene nanoribbon(BPNR)stack.Our calculations find that the electronic conductance and power factor can be strongly enhanced by the BPNR stack,and their enhancements can be further observed with the twist between the layers.The main reason for this is the electronic hybridization between the layers can provide new transport channels,and the twist can modulate the strength of interlayer electronic hybridization,resulting in extremely violent fluctuations in electron transmission and hence an enhanced power factor.While the phonon thermal conductance exhibits very low dependence on the layer stack and twist.Combining these factors,our results reveal that the thermoelectric performance can be greatly modulated and enhanced in twist bilayer BPNRHJ:the figure of merit will be over 2.5 in 4-4-ZBPNR@ZGNR-AA-8.8∘at 500 K.
基金financially supported by the National Natural Science Foundation of China(Nos.51302079,51702138 and 51403193)the Natural Science Foundation of Hunan Province(No.2017JJ1008)the Key Research and Development Program of Hunan Province of China(No.2018GK2031)。
文摘The electrochemical ammonia synthesis has attracted increasing attention due to its energy saving characteristics.However,developing novel electrocatalysts and their mechanism remain great challenges.Here,several transition metal(TM)atoms doped on phosphorene were studied as N2 fixation electrocatalysts by using density functional theory(DFT)calculations.The results demonstrate that single Ru atom doped phosphorene shows an excellent catalytic activity for ammonia synthesis via the enzymatic pattern.A small overpotential of 0.696 V is achieved for this process.The effect of oxidation in the catalyst was also discussed in our work.Oxidation deactivates the catalyst,which should be avoided in the experiment.Our outcomes offer a novel perspective for single-atom catalytic ammonia synthesis with phosphorene as a substrate.
基金financially supported by the National Natural Science Foundation of China(21902051,21861130353,U1905214,21961142019,22032002,21761132002,and 21425309)the Fundamental Research Funds for the Central Universities(ZQN-807)+7 种基金the Natural Science Foundation of Fujian Province(2019J05090 and 2017J01014)the Graphene Powder and Composite Research Center of Fujian Province(2017H2001)the Scientific Research Funds of Huaqiao University(20171XD033)the Open Project Program of the State Key Laboratory of Photocatalysis on Energy and Environment of Fuzhou University(SKLPEE-KF201803)the National Key Technologies R&D Program of China(2018YFA0209301)the National Basic Research Program of China(2013CB632405)the Chang Jiang Scholars Program of China(T2016147)the 111 Project(D16008).
文摘Semiconductor photocatalysis is a potential pathway to solve the problems of global energy shortage and environmental pollution.Black phosphorus(BP)has been widely used in the field of photocatalysis owing to its features of high hole mobility,adjustable bandgap,and wide optical absorption range.Nevertheless,pristine BP still exhibits unsatisfactory photocatalytic activity due to the low separation efficiency of photoinduced charge carriers.In recent years,the construction of heterostructured photocatalysts based on BP has become a research hotspot in photocatalysis with the remarkable improvement of photoexcited charge-separation efficiency.Herein,progress on the design,synthesis,properties,and applications of BP and its corresponding heterostructured photocatalysts is summarized.Furthermore,the photocatalytic applications of BP-based heterostructured photocatalysts in water splitting,pollutant degradation,carbon dioxide reduction,nitrogen fixation,bacterial disinfection,and organic synthesis are reviewed.Opportunities and challenges for the exploration of advanced BP-based heterostructured photocatalysts are presented.This review will promote the development and applications of BP-based heterostructured photocatalysts in energy conversion and environmental remediation.
基金supported by the National Natural Science Foundation of China (Nos. 21701043, 21573066, 51402100)the Provincial Natural Science Foundation of Hunan (Nos 2016JJ1006, 2016TP1009)the Key Laboratory of Optoelectronic Devices and Systems of Ministry of Education and Guangdong Province and Shenzhen Science and Technology Program (No JCYJ20170306141659388)
文摘First-principles calculations based on van der Waals(vdW) corrected density functional theory(DFT) are firstly employed to investigate the adsorption of methanol(CH_3OH) gas molecule on pristine and Xdoped phosphorene( =B, C, N and O). The CH_3OH gas molecule is placed on the top of different phosphorene surfaces, the whole adsorption systems are fully optimized by using Vienna ab initio simulation package(VASP). The calculation results demonstrate that both pristine and heteroatomdoped phosphorene are sensitive to CH_3OH gas molecule with a moderate adsorption energy and an excellent charge transfer. Among all the investigated adsorption configurations, CH_3OH gas molecule is physically absorbed on pristine phosphorene and heteroatom-doped phosphorene. The N and O doping improve the adsorption of phosphorene with CH_3OH gas molecule, while B and C doping are almost not beneficial compared to the pristine phosphorene. The results suggest that N-doped and O-doped phosphorene are ideal candidates used for CH_3OH gas sensing.
基金Project supported by the National Natural Science Foundation of China(Grant Nos.11574080 and 91833302)。
文摘We investigate the electronic and transport properties of one-dimensional armchair phosphorene nanoribbons(APNRs) containing atomic vacancies with different distributions and concentrations using ab initio density functional calculations. It is found that the atomic vacancies are easier to form and detain at the edge region rather than a random distribution through analyzing formation energy and diffusion barrier. The highly local defect states are generated at the vicinity of the Fermi level, and emerge a deep-to-shallow transformation as the width increases after introducing vacancies in APNRs.Moreover, the electrical transport of APNRs with vacancies is enhanced compared to that of the perfect counterparts. Our results provide a theoretical guidance for the further research and applications of PNRs through defect engineering.
基金Project supported by the State Key Program for Basic Researches of China(Grant No.2014CB921103)the Natural Science Foundation of Jiangsu Province,China(Grant Nos.BK20141441 and BK2010012)
文摘According to first-principles calculations, it is our prediction that bilayer phosphorene（BLP） will become a quasitwo-dimensional superconductor under a certain degree of interlayer compression. A decreasing interlayer distance may realize the transition in the BLP from a semiconducting phase to a metallic phase. On the other hand, a severe vertical compression may make the BLP lattice become dynamically unstable. It is found that in the stable metallic phase of the BLP, interlayer phonon modes dominate the electron-phonon coupling λ. The obtained λ can be greater than 1 and the superconducting temperature T_c can be higher than 10 K.
基金supported by the National Natural Science Foundation of China (No.21473168 and No.21873088)the Natural Science Foundation of the Anhui Higher Education Institutions (No.KJ2016A144)
文摘As a clean and renewable future energy source, hydrogen fuel can be produced via solar water splitting. Two-dimensional (2D) black phosphorene (black-P) can harvest visible light due to the desirable band gap, which promises it as a metal-free photocatalyst. However, black-P can be only used to produce hydrogen since the oxidation potential of water locates lower than the position of the valence band maximum. To improve the photocatalytic performance of black-P, here, using black-P and blue phosphorene (blue-P) monolayers, we propose a 2D van der Waals (vdW) heterojunction. Theoretical results, including the band structures, density of states, Bader charge population, charge density di erence, and optical absorption spectra, clearly reveal that the visible light absorption ability is obviously improved, and the band edge alignment of the proposed vdW heterojunction displays a typical type-II feature to effectively separate the photogenerated carriers. At the same time, the built-in interfacial electric field prevents the electron-hole recombination. These predictions suggest that the examined phosphorene-based vdW heterojunction is an efficient photocatalyst for solar water splitting.
基金Project supported by the National Natural Science Foundation of China(Grant Nos.11774100 and 11474106)
文摘Strain is a powerful tool to engineer the band structure of bilayer phosphorene.The band gap can be decreased by vertical tensile strain or in-plane compressive strain.At a critical strain,the gap is closed and the bilayer phosphorene is turn to be a semi-Dirac semimetal material.If the strain is stronger than the criterion,a band-inversion occurs and it re-happens when the strain is larger than another certain value.For the zigzag bilayer phosphorene ribbon,there are two edge band dispersions and each dispersion curve represents two degenerate edge bands.When the first band-inversion happens,one of the edge band dispersion disappears between the band-cross points while the other survives,and the latter will be eliminated between another pair of band-cross points of the second band-inversion.The optical absorption of bilayer phosphorene is highly polarized along armchair direction.When the strain is turn on,the optical absorption edge changes.The absorption rate for armchair polarized light is decreased by gap shrinking,while that for zigzag polarized light increases.The bandtouch and band-inversion respectively result in the sublinear and linear of absorption curve versus light frequency in low frequency limit.
基金Supported by the National Natural Science Foundation of China under Grant No 11374002the Scientific Research Fund of Hunan Provincial Education Department under Grant No 17A001the Hunan Provincial Key Laboratory of Flexible Electronic Materials Genome Engineering of Changsha University of Science and Technology
文摘We demonstrate theoretically the anisotropic quantum transport of electrons through an electric field on monolayer and multilayer phosphorene. Using the long-wavelength Hamiltonian with continuum approximation, we find that the transmission probability for transport through an electric field is an oscillating function of incident angle, electric field intensity, as well as the incident energy of electrons. By tuning the electric field intensity and incident angle, the channels can be transited from opaque to transparent. The conductance through the quantum waveguides depends sensitively on the transport direction because of the anisotropic effective mass, and the anisotropy of the conductance can be tuned by the electric field intensity and the number of layers. These behaviors provide us an efficient way to control the transport of phosphorene-based microstructures.
基金Supported by the National Natural Science Foundation of China under Grant No 11374002the Hunan Provincial Natural Science Foundation of China under Grant No 13JJ2026+2 种基金the Scientific Research Fund of Hunan Provincial Education Department under Grant No 12B010the Science and Technology Innovative Research Team in Higher Educational Institutions of Hunan Provincethe Construct Program of the Key Discipline in Hunan Province
文摘We demonstrate theoretically the anisotropic quantum transport of electrons through a single barrier on monolayer phosphorene. Using an effective k .p Hamiltonian, we find that the transmission probability for transport through n-n-n （or n p-n） junction is an oscillating function of the incident angle, the barrier height, as well as the incident energy of electrons. The conductance in such systems depends sensitively on the transport direction due to the anisotropic effective mass. By tuning the Fermi energy and gate voltage, the channels can be transited from opaque to transparent, which provides us with an efficient way to control the transport of monolayer phosphorene-based microstructures.
基金the National Natural Science Foundation of China (No.21573204 and No.21421063)Ministry of Science and Technology of China (2018YFA0208603 and 2016YFA0200602)Anhui Initiative in Quantum Information Technologies, the Fundamental Research Funds for the Central UniversitiesUniversities, the National Program for Support of Top-notch Young Professional, Chinese Academy of Sciences Interdisciplinary Innovation Team, and Super Computer Center of USTC supercomputing center and CAS supercomputing center.
文摘Searching alternatives to Pt-based catalyst for producing hydrogen via water splitting has gathered enormous attention to develop renewable energy. Phosphorene has been investigated widely for its large surface area, low cost, and high carrier mobility, however, the poor activity in hydrogen evolution reaction (HER) and low conductivity limit its practical application. Herein, on the basis of first-principles calculations, we demonstrate that the catalytic HER in phosphorene can be enhanced significantly with cobalt intercalations. The Co-intercalated phosphorene is metallic with charge transfer from Co atoms to phosphorene, which could enhance the catalytic activity of phosphorene. In addition, the calculated Gibbs free energy of hydrogen adsorption on Co-intercalated phosphorene bilayer is comparable to that on Pt(111) surface, independent of the degree of hydrogen coverage. Our study implies that the Co intercalation provides an effective approach to enhance the catalytic HER in phosphorene.
基金financially supported by the National Key Research and Development Program of China(No.2017YFB1002900)the National Natural Science Foundation of China(No.51661145021)+5 种基金the Key Natural Science Program of Jiangsu Province(Nos.BE2022118,BE2021643 and BE2016772)the Traction Project of Key Laboratory of Advanced Carbon Materials and Wearable Energy Technologies of Jiangsu Province(No.Q816000217)the Scholarship from Key Laboratory of Modern Optical Technologies of Ministry of Education of Chinathe Priority Academic Program Development(PAPD)of Jiangsu Higher Education InstitutionsChina Prosperity Green Industry Foundation of Ministry of Industry and Information Technologysupported by the open project of synchrotron radiation characterization of chain oriented/stacked polar topology and energy modulation of supramolecules(No.2100982)。
文摘Black phosphorus with a superior theoretical capacity(2596 mAh g^(-1))and high conductivity is regarded as one of the powerful candidates for lithium-ion battery(LIB)anode materials,whereas the severe volume expansion and sluggish kinetics still impede its applications in LIBs.By contrast,the exfoliated two-dimensional phosphorene owns negligible volume variation,and its intrinsic piezoelectricity is considered to be beneficial to the Li-ion transfer kinetics,while its positive influence has not been discussed yet.Herein,a phosphorene/MXene heterostructure-textured nanopiezocomposite is proposed with even phosphorene distribution and enhanced piezo-electrochemical coupling as an applicable free-standing asymmetric membrane electrode beyond the skin effect for enhanced Li-ion storage.The experimental and simulation analysis reveals that the embedded phosphorene nanosheets not only provide abundant active sites for Li-ions,but also endow the nanocomposite with favorable piezoelectricity,thus promoting the Li-ion transfer kinetics by generating the piezoelectric field serving as an extra accelerator.By waltzing with the MXene framework,the optimized electrode exhibits enhanced kinetics and stability,achieving stable cycling performances for 1,000 cycles at 2 A g^(-1),and delivering a high reversible capacity of 524 m Ah g^(-1)at-20℃,indicating the positive influence of the structural merits of self-assembled nanopiezocomposites on promoting stability and kinetics.
文摘Phosphorene is a two-dimensional semiconductor with layers-dependent bandgap in the near-infrared range and it has attracted a great deal of attention due to its high anisotropy and cartier mobility. The highly anisotropic nature of phos- phorene has been demonstrated through Raman and polarization photoluminescence measurements. Photoluminescence spectroscopy has also revealed the layers-dependent bandgap of phosphorene. Furthermore, due to the reduced dimension- ality and screening in phosphorene, excitons and trions can stably exist at elevated temperatures and have large binding energies. The exciton and trion dynamics are thus detected by applying electrical bias or optical injection to the phospho- rene system. Finally, various optical and optoelectronic applications based on phosphorene have been demonstrated and discussed.
基金Projected supported by the National Natural Science Foundation of China(Grant No.11574167)the New Century 151 Talents Project of Zhejiang Province,Chinathe K.C.Wong Magna Foundation in Ningbo University,China
文摘We have studied the structural and electronic properties of a hybrid hexagonal boron nitride with phosphorene nanocomposite using ab initio density functional calculations. It is found that the interaction between the hexagonal boron nitride and phosphorene is dominated by the weak van der Waals interaction, with their own intrinsic electronic properties preserved. Furthermore, the band gap of the nanocomposite is dependent on the interfacial distance. Our results could shed light on the design of new devices based on van der Waals heterostructure.
基金supported by the National Key Research and Development Program of China(No.2019YFE0118800)National Natural Science Foundation of China(Nos.22005215,21773124)+1 种基金Tianjin Science and Technology Project(No.19YFSLQY00070)Hebei Province Innovation Ability Promotion Project(Nos.20544401D,20312201D)。
文摘As an important anode material for fast-charging Li-ion batteries(LIBs),black phosphorus(BP)has attracted extensive attention.Black phosphorene nanotubes(BPNTs)can be theoretically produced by rolling up the black phosphorene nanosheet along armchair(a-BPNTs)and zigzag(z-BPNTs)directions.The effects of curvature,chirality,Li-storage concentrations and strain stress on the Li-storage performance such as Li diffusion barriers and mechanical stabilities of BPNTs are mainly investigated by first principles calculations.The theoretical calculations predict that the a-BPNTs and z-BPNTs have good maximum Li-storage capacities,and the z-BPNTs exhibit better flexibility than a-BPNTs.The mechanical stabilities and Li-migration are all related to the curvature of BPNTs.Additionally,both a-BPNTs and z-BPNTs exhibit fast Li-ion conductivity along the c-axis direction.Moreover,the average Poisson's ratio of a-BPNTs(0.68)is larger than that of z-BPNTs(0.17),indicating that the strain stress is more difficult to apply on a-BPNTs than z-BPNTs.Our calculations predict that the a-BPNTs can afford ultrafast kinetic rate for fastcharging and high-power LIBs,while the z-BPNTs can provide extra capacity for high-energy LIBs.
基金financially supported by the Natural Science Funds (NSF) for Distinguished Young Scholar of Heilongjiang Province (No. JC2018004)。
文摘Superior bifunctional electrocatalysts with ultra-high stability and excellent efficiency are crucial to boost the oxygen evolution reaction(OER) and the hydrogen evolution reduction(HER) in the overall water splitting(OWS) for the sustainable production of clean fuels. Herein, comprehensive density functional theory(DFT) computations were performed to explore the potential of several single transition metal(TM) atoms anchored on various S-doped black phosphorenes(TM/Snx-BP) for bifunctional OWS electrocatalysis. The results revealed that these candidates display good stability, excellent electrical conductivity, and diverse spin moments. Furthermore, the Rh/S12-BP catalyst was identified as an eligible bifunctional catalyst for OWS process due to the low overpotentials for OER(0.43 V) and HER(0.02 V), in which Rh and its adjacent P atoms were identified as the active sites. Based on the computed Gibbs free energies of OH~*, O~*, OOH~* and H~*, the corresponding volcano plots for OER and HER were established.Interestingly, the spin moments and the charge distribution of the active sites determine the catalytic trends of OER and HER. Our findings not only propose a promising bifunctional catalyst for OWS, but also widen the potential application of BP in electrocatalysis.
基金Project supported by the National Natural Science Foundation of China(Grant No.11564008)the Natural Science Foundation of Guangxi Zhuang Autonomous Region,China(Grant No.2017GXNSFAA198195)the Shanghai Supercomputer Center。
文摘We have investigated the electronic and magnetic properties of zigzag phosphorene nanoribbons(ZPNRs)with transition metal(TM)passivated atoms,it can be found that the ZPNRs with TM passivated atoms exhibit different magnetisms except for the Ni-passivated system.Meanwhile,the results show that the magnetic moments of ZPNRs with TM passivated atoms are larger than that of ZPNRs with other passivated non-metals/groups.Interestingly,it can be found that Fe-passivated ZPNR exhibits magnetic semiconducting character,which provides the possbility for the application of phosphorene in information storage.For Mn-passivated ZPNRs,it exhibits the half-metallicity.These results may be useful for potential applications of phosphorene in electronic and high-performance spintronic devices.
基金supported by the National Natural Science Foundation of China (NSFC, Nos. 51972312 and U20A20242)the Natural Science Foundation of Liaoning Province of China (No. 2020-MS-003)。
文摘The synthesis of high-value multi-carbon products through the electrochemical reduction of carbon monoxide(COER) is one of the promising avenues for carbon utilization and energy storage,in which searching for efficient electrocatalysts that exhibit moderate CO intermediate binding strength and low kinetic barrier for C-C coupling is a key issue.Herein,by means of comprehensive density functional theory(DFT) computations,we theoretically designed three synergistic coupling catalysts by co-doping transition metal(TM=Fe,Co and Ni) and boron(B) into the two-dimensional black phosphorene(BP),namely TMB@BP for COER to C_(2) products.DFT computations and ab initio molecular dynamics simulations reveal the good stability and high feasibility of these proposed TM-B@BP catalysts for practical applications and future experimental synthesis.More interestingly,high-value ethylene(C_(2)H_(4)),ethane(C_(2)H_(6)) and ethanol(C_(2)H_(5)OH) products can be obtained on these three designed electrocatalysts with ultra-small limiting potentials(-0.20~-0.41 V) and low kinetic energy barriers of C-C coupling(0.52~0.91 eV).Meanwhile,the competitive one-carbon(C_(1)) products and hydrogen evolution reaction can also be effectively suppressed.The promising activity and selectivity of these three designed electrocatalysts render them ideal candidates for CO electroreduction,thus providing a cost-effective opportunity to achieve a sustainable production of high value C_(2) chemicals and fuels.
基金This work was supported by the National Natural Science Foundation of China(No.21825302 and No.21903076)the Taishan Scholar Program of Shandong Province of China(tsqn201909122)We also thank Supercomputing Center of USTC(USTC-SCC),Supercomputing Center of the Chinese Academy of Sciences(SCCAS),Tianjin Supercomputer Center,Guangzhou Supercomputer Center,and the Shanghai Supercomputer Center.
文摘There is an ideal desire to develop the high-performance anodes materials for Liion batteries(LIBs),which requires not onlyhigh stability and reversibility,but also rapidcharging/discharging rate.In this work,webuiltablue phosphorene-graphene(BlueP-G)intralayer heterostructure by connecting BlueP and graphene monolayers at zigzag edges with covalent bonds.Based on the density functional theory simulation,the electronic structure of the heterostructure,Li adsorption and Li diffusion on heterostructure were systematically investigated.Compared with the pristine BlueP,the existence of graphene layer increases the overall conductivity of BlueP-G intralayer heterostructure.The significantly enhanced adsorption energy indicates the Li deposition on anode surface is energetically favored.The fast diffusion of Li with energy barrier as low as 0.02-0.09 eV indicates the growth of Li dendrite could be suppressed and the stability and reversibility of the battery will be increased.With a combination of increased conductivity of electronic charge,excellent Li adsorption and Li mobility on surface,BlueP-G intralayer heterostructure with zigzag interface is quite promising in the application of anode material for Li-ion batteries.
