The design of cost-effective and efficient metal-free carbon-based catalysts for the hydrogen evolution reaction(HER)is of great significance for increasing the production of clean hydrogen by the electrolysis of alka...The design of cost-effective and efficient metal-free carbon-based catalysts for the hydrogen evolution reaction(HER)is of great significance for increasing the production of clean hydrogen by the electrolysis of alkaline water.Precise control of the electronic structure by heteroatom doping has proven to be efficient for increasing catalytic activity.Nevertheless,both the structural characteristics and the underlying mechanism are not well understood,especially for doping with two different atoms,thus limiting the use of these catalysts.We report the production of phosphorus and nitrogen co-doped hollow carbon nanospheres(HCNs)by the copolymerization of pyrrole and aniline at a Triton X-100 micelle-interface,followed by doping with phytic acid and carbonization.The unique pore structure and defect-rich framework of the HCNs expose numerous active sites.Crucially,the combined effect of graphitic nitrogen and phosphorus-carbon bonds modulate the local electronic structure of adjacent C atoms and facilitates electron transfer.As a res-ult,the HCN carbonized at 1100°C exhibited superior HER activity and an outstanding stability(70 h at a current density of 10 mA cm^(−2))in alkaline water,because of the large number of graphitic nitrogen and phosphorus-carbon bonds.展开更多
Solid oxide electrolysis cells(SOECs)can effectively convert CO_(2)into high value-added CO fuel.In this paper,Sc-doped Sr_(2)Fe_(1.5)Mo_(0.3)Sc_(0.2)O_(6−δ)(SFMSc)perovskite oxide material is synthesized via solid-p...Solid oxide electrolysis cells(SOECs)can effectively convert CO_(2)into high value-added CO fuel.In this paper,Sc-doped Sr_(2)Fe_(1.5)Mo_(0.3)Sc_(0.2)O_(6−δ)(SFMSc)perovskite oxide material is synthesized via solid-phase method as the cathode for CO_(2)electrolysis by SOECs.XRD confirms that SFMSc exhibits a stable cubic phase crystal structure.The experimental results of TPD,TG,EPR,CO_(2)-TPD further demonstrate that Sc-doping increases the concentration of oxygen vacancy in the material and the chemical adsorption capacity of CO_(2)molecules.Electrochemical tests reveal that SFMSc single cell achieves a current density of 2.26 A/cm^(2) and a lower polarization impedance of 0.32Ω·cm^(2) at 800°C under the applied voltage of 1.8 V.And no significant performance attenuation or carbon deposition is observed after 80 h continuous long-term stability test.This study provides a favorable support for the development of SOEC cathode materials with good electro-catalytic performance and stability.展开更多
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 interac-tions(EMSIs).In the styrene hydroformylation reaction,the activity of Rh_(1)/PCN single-atom catalysts(SACs)with vary-ing 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
We used the natural product chamomile as a carbon source to synthesize praseodymium(Pr) and nitrogen(N) co-doped biomass carbon dots(Pr/N-BCDs) with remarkable luminescence properties by one-step hydrothermal method.C...We used the natural product chamomile as a carbon source to synthesize praseodymium(Pr) and nitrogen(N) co-doped biomass carbon dots(Pr/N-BCDs) with remarkable luminescence properties by one-step hydrothermal method.Compared with single N-doped BCDs(N-BCDs) and Pr-doped BCDs(Pr-BCDs),Pr/N-BCDs not only showed better fluorescence properties and stability but also achieved a significant increase in quantum yield of 12%.More importantly,under certain conditions,Pr/N-BCDs and 2,4-dinitrophenylhydrazide(2,4-DNPH) had significant fluorescence internal filtration effect(IFE) and dynamic quenching effect,and in the concentration range of0.50-20 μmol·L^(-1),the concentration of 2,4-DNPH had a good linear relationship with the fluorescence quenching signal,and the detection limit was as low as 2.1 nmol·L^(-1).展开更多
The accepted doping ion in Ti^(4+)-site of PbZr_(y)Ti_(1–y)O_(3)(PZT)-based piezoelectric ceramics is a well-known method to increase mechanical quality factor(Q_(m)),since the acceptor coupled by oxygen vacancy beco...The accepted doping ion in Ti^(4+)-site of PbZr_(y)Ti_(1–y)O_(3)(PZT)-based piezoelectric ceramics is a well-known method to increase mechanical quality factor(Q_(m)),since the acceptor coupled by oxygen vacancy becomes defect dipole,which prevents the domain rotation.In this field,a serious problem is that generally,Qm decreases as the temperature(T)increases,since the oxygen vacancies are decoupled from the defect dipoles.In this work,Q_(m) of Pb_(0.95)Sr_(0.05)(Zr_(0.53)Ti_(0.47))O_(3)(PSZT)ceramics doped by 0.40%Fe_(2)O_(3)(in mole)abnormally increases as T increases,of which the Qm and piezoelectric coefficient(d_(33))at room temperature and Curie temperature(TC)are 507,292 pC/N,and 345℃,respectively.The maximum Qm of 824 was achieved in the range of 120–160℃,which is 62.52%higher than that at room temperature,while the dynamic piezoelectric constant(d_(31))was just slightly decreased by 3.85%.X-ray diffraction(XRD)and piezoresponse force microscopy results show that the interplanar spacing and the fine domains form as temperature increases,and the thermally stimulated depolarization current shows that the defect dipoles are stable even the temperature up to 240℃.It can be deduced that the aggregation of oxygen vacancies near the fine domains and defect dipole can be stable up to 240℃,which pins domain rotation,resulting in the enhanced Q_(m) with the increasing temperature.These results give a potential path to design high Q_(m) at high temperature.展开更多
Nitrogen doping has been widely used to improve the performance of carbon electrodes in supercapacitors,particularly in terms of their high-frequency response.However,the charge storage and electrolyte ion response me...Nitrogen doping has been widely used to improve the performance of carbon electrodes in supercapacitors,particularly in terms of their high-frequency response.However,the charge storage and electrolyte ion response mechanisms of different nitrogen dopants at high frequencies are still unclear.In this study,melamine foam carbons with different configurations of surfacedoped N were formed by gradient carbonization,and the effects of the configurations on the high-frequency response behavior of the supercapacitors were analyzed.Using a combination of experiments and first-principle calculations,we found that pyrrolic N,characterized by a higher adsorption energy,increases the charge storage capacity of the electrode at high frequencies.On the other hand,graphitic N,with a lower adsorption energy,increases the speed of ion response.We propose the use of adsorption energy as a practical descriptor for electrode/electrolyte design in high-frequency applications,offering a more universal approach for improving the performance of N-doped carbon materials in supercapacitors.展开更多
The lattice-matched XBn structures of InAsSb,grown on GaSb substrates,exhibit high crystal quali⁃ty,and can achieve extremely low dark currents at high operating temperatures(HOT).Its superior performance is attribute...The lattice-matched XBn structures of InAsSb,grown on GaSb substrates,exhibit high crystal quali⁃ty,and can achieve extremely low dark currents at high operating temperatures(HOT).Its superior performance is attributed to the unipolar barrier,which blocks the majority carriers while allowing unhindered hole transport.To further explore the energy band and carrier transport mechanisms of the XBn unipolar barrier structure,this pa⁃per systematically investigates the influence of doping on the dark current,photocurrent,and tunneling character⁃istics of InAsSb photodetectors in the PBn structure.Three high-quality InAsSb samples with unintentionally doped absorption layers(AL)were prepared,with varying p-type doping concentrations in the GaSb contact layer(CL)and the AlAsSb barrier layer(BL).As the p-type doping concentration in the CL increased,the device’s turn-on bias voltage also increased,and p-type doping in the BL led to tunneling occurring at lower bias voltages.For the sample with UID BL,which exhibited an extremely low dark current of 5×10^(-6) A/cm^(2).The photocurrent characteristics were well-fitted using the back-to-back diode model,revealing the presence of two opposing space charge regions on either side of the BL.展开更多
The response wavelength of the blocked-impurity-band(BIB)structured infrared detector can reach 200µm,which is the most important very long wavelength infrared astronomical detector.The ion implantation method gr...The response wavelength of the blocked-impurity-band(BIB)structured infrared detector can reach 200µm,which is the most important very long wavelength infrared astronomical detector.The ion implantation method greatly simplifies the fabrication process of the device,but it is easy to cause lattice damage,introduce crystalline defects,and lead to the increase of the dark current of detectors.Herein,the boron-doped germanium ion implantation process was studied,and the involved lattice damage mechanism was discussed.Experimental conditions involved using 80 keV energy for boron ion implantation,with doses ranging from 1×10^(13)cm^(-2)to 3×10^(15)cm^(-2).After implantation,thermal annealing at 450℃was implemented to optimize dopant activation and mitigate the effects of ion implantation.Various sophisticated characterization techniques,including X-ray dif⁃fraction(XRD),Raman spectroscopy,X-ray photoelectron spectroscopy(XPS),and secondary ion mass spec⁃trometry(SIMS)were used to clarify lattice damage.At lower doses,no notable structural alterations were ob⁃served.However,as the dosage increased,specific micro distortions became apparent,which could be attributed to point defects and residual strain.The created lattice damage was recovered by thermal treatment,however,an irreversible strain induced by implantation still existed at heavily dosed samples.展开更多
The capacitive performance of carbon materials as supercapacitor electrode is synergistically influenced by the surface porous structure,graphitization structure,and surface atomic doping.However,simple realization of...The capacitive performance of carbon materials as supercapacitor electrode is synergistically influenced by the surface porous structure,graphitization structure,and surface atomic doping.However,simple realization of their synergistic regulation still faces significant challenges.Based on the biological porous structure,heteroatom-rich content and low cost of chestnut,this work adopt chestnut as precursor to prepare carbon electrode,of which the pores,graphitization,and surface atomic doping are synergistically regulated by simply changing the activation temperature.The optimized carbon electrode possesses a hierarchical porous structure with partial graphitization and O and N co doping.Benefited from these merits,the chestnut-derived porous carbon as a supercapacitor electrode,can achieve a high specific capacitance of 328.6 F/g at 1 A/g,which still retains 80.8%when the current density enlarging to 20 A/g.By packaging the symmetric electric double-layer capacitor,the device exhibits a specific capacitance of 63.6 F/g at 1 A/g,delivering an energy density of 12.7 W·h/kg at a power density of 600 W/kg.The stability of the device is tested at a current density of 20 A/g,which shows a capacitance retention rate of up to 90%after 10000 charge-discharge cycles.展开更多
基金financially supported by the project of the National Natural Science Foundation of China(52322203)the Key Research and Development Program of Shaanxi Province(2024GHZDXM-21)。
文摘The design of cost-effective and efficient metal-free carbon-based catalysts for the hydrogen evolution reaction(HER)is of great significance for increasing the production of clean hydrogen by the electrolysis of alkaline water.Precise control of the electronic structure by heteroatom doping has proven to be efficient for increasing catalytic activity.Nevertheless,both the structural characteristics and the underlying mechanism are not well understood,especially for doping with two different atoms,thus limiting the use of these catalysts.We report the production of phosphorus and nitrogen co-doped hollow carbon nanospheres(HCNs)by the copolymerization of pyrrole and aniline at a Triton X-100 micelle-interface,followed by doping with phytic acid and carbonization.The unique pore structure and defect-rich framework of the HCNs expose numerous active sites.Crucially,the combined effect of graphitic nitrogen and phosphorus-carbon bonds modulate the local electronic structure of adjacent C atoms and facilitates electron transfer.As a res-ult,the HCN carbonized at 1100°C exhibited superior HER activity and an outstanding stability(70 h at a current density of 10 mA cm^(−2))in alkaline water,because of the large number of graphitic nitrogen and phosphorus-carbon bonds.
基金supported by National Key R&D Program of China(2021YFB4001401)National Natural Science Foundation of China(52272190,22178023).
文摘Solid oxide electrolysis cells(SOECs)can effectively convert CO_(2)into high value-added CO fuel.In this paper,Sc-doped Sr_(2)Fe_(1.5)Mo_(0.3)Sc_(0.2)O_(6−δ)(SFMSc)perovskite oxide material is synthesized via solid-phase method as the cathode for CO_(2)electrolysis by SOECs.XRD confirms that SFMSc exhibits a stable cubic phase crystal structure.The experimental results of TPD,TG,EPR,CO_(2)-TPD further demonstrate that Sc-doping increases the concentration of oxygen vacancy in the material and the chemical adsorption capacity of CO_(2)molecules.Electrochemical tests reveal that SFMSc single cell achieves a current density of 2.26 A/cm^(2) and a lower polarization impedance of 0.32Ω·cm^(2) at 800°C under the applied voltage of 1.8 V.And no significant performance attenuation or carbon deposition is observed after 80 h continuous long-term stability test.This study provides a favorable support for the development of SOEC cathode materials with good electro-catalytic performance and stability.
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 interac-tions(EMSIs).In the styrene hydroformylation reaction,the activity of Rh_(1)/PCN single-atom catalysts(SACs)with vary-ing 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 the National Natural Science Foundation of China (Grant No.22063010)the Natural Science Foundation of Shaanxi Province (Grant No.2022QFY07-05)Yan'an Science and Technology Plan Project (Grants No.2022SLJBZ-002, 2023-CYL-193)。
文摘We used the natural product chamomile as a carbon source to synthesize praseodymium(Pr) and nitrogen(N) co-doped biomass carbon dots(Pr/N-BCDs) with remarkable luminescence properties by one-step hydrothermal method.Compared with single N-doped BCDs(N-BCDs) and Pr-doped BCDs(Pr-BCDs),Pr/N-BCDs not only showed better fluorescence properties and stability but also achieved a significant increase in quantum yield of 12%.More importantly,under certain conditions,Pr/N-BCDs and 2,4-dinitrophenylhydrazide(2,4-DNPH) had significant fluorescence internal filtration effect(IFE) and dynamic quenching effect,and in the concentration range of0.50-20 μmol·L^(-1),the concentration of 2,4-DNPH had a good linear relationship with the fluorescence quenching signal,and the detection limit was as low as 2.1 nmol·L^(-1).
基金National Natural Science Foundation of China(U2241242)National Key R&D Program of China(2023YFB3812000,2021YFA0716502)。
文摘The accepted doping ion in Ti^(4+)-site of PbZr_(y)Ti_(1–y)O_(3)(PZT)-based piezoelectric ceramics is a well-known method to increase mechanical quality factor(Q_(m)),since the acceptor coupled by oxygen vacancy becomes defect dipole,which prevents the domain rotation.In this field,a serious problem is that generally,Qm decreases as the temperature(T)increases,since the oxygen vacancies are decoupled from the defect dipoles.In this work,Q_(m) of Pb_(0.95)Sr_(0.05)(Zr_(0.53)Ti_(0.47))O_(3)(PSZT)ceramics doped by 0.40%Fe_(2)O_(3)(in mole)abnormally increases as T increases,of which the Qm and piezoelectric coefficient(d_(33))at room temperature and Curie temperature(TC)are 507,292 pC/N,and 345℃,respectively.The maximum Qm of 824 was achieved in the range of 120–160℃,which is 62.52%higher than that at room temperature,while the dynamic piezoelectric constant(d_(31))was just slightly decreased by 3.85%.X-ray diffraction(XRD)and piezoresponse force microscopy results show that the interplanar spacing and the fine domains form as temperature increases,and the thermally stimulated depolarization current shows that the defect dipoles are stable even the temperature up to 240℃.It can be deduced that the aggregation of oxygen vacancies near the fine domains and defect dipole can be stable up to 240℃,which pins domain rotation,resulting in the enhanced Q_(m) with the increasing temperature.These results give a potential path to design high Q_(m) at high temperature.
文摘Nitrogen doping has been widely used to improve the performance of carbon electrodes in supercapacitors,particularly in terms of their high-frequency response.However,the charge storage and electrolyte ion response mechanisms of different nitrogen dopants at high frequencies are still unclear.In this study,melamine foam carbons with different configurations of surfacedoped N were formed by gradient carbonization,and the effects of the configurations on the high-frequency response behavior of the supercapacitors were analyzed.Using a combination of experiments and first-principle calculations,we found that pyrrolic N,characterized by a higher adsorption energy,increases the charge storage capacity of the electrode at high frequencies.On the other hand,graphitic N,with a lower adsorption energy,increases the speed of ion response.We propose the use of adsorption energy as a practical descriptor for electrode/electrolyte design in high-frequency applications,offering a more universal approach for improving the performance of N-doped carbon materials in supercapacitors.
基金Supported by the Candidate Talents Training Fund of Yunnan Province(202205AC160054)the National Natural Science Foundation of China(62174156)。
文摘The lattice-matched XBn structures of InAsSb,grown on GaSb substrates,exhibit high crystal quali⁃ty,and can achieve extremely low dark currents at high operating temperatures(HOT).Its superior performance is attributed to the unipolar barrier,which blocks the majority carriers while allowing unhindered hole transport.To further explore the energy band and carrier transport mechanisms of the XBn unipolar barrier structure,this pa⁃per systematically investigates the influence of doping on the dark current,photocurrent,and tunneling character⁃istics of InAsSb photodetectors in the PBn structure.Three high-quality InAsSb samples with unintentionally doped absorption layers(AL)were prepared,with varying p-type doping concentrations in the GaSb contact layer(CL)and the AlAsSb barrier layer(BL).As the p-type doping concentration in the CL increased,the device’s turn-on bias voltage also increased,and p-type doping in the BL led to tunneling occurring at lower bias voltages.For the sample with UID BL,which exhibited an extremely low dark current of 5×10^(-6) A/cm^(2).The photocurrent characteristics were well-fitted using the back-to-back diode model,revealing the presence of two opposing space charge regions on either side of the BL.
基金Supported by National Key R&D Program of China(2023YFA1608701)National Natural Science Foundation of China(62274168,11933006,U2141240)Hangzhou Leading Innovation and Entrepreneurship Team(TD2020002)。
文摘The response wavelength of the blocked-impurity-band(BIB)structured infrared detector can reach 200µm,which is the most important very long wavelength infrared astronomical detector.The ion implantation method greatly simplifies the fabrication process of the device,but it is easy to cause lattice damage,introduce crystalline defects,and lead to the increase of the dark current of detectors.Herein,the boron-doped germanium ion implantation process was studied,and the involved lattice damage mechanism was discussed.Experimental conditions involved using 80 keV energy for boron ion implantation,with doses ranging from 1×10^(13)cm^(-2)to 3×10^(15)cm^(-2).After implantation,thermal annealing at 450℃was implemented to optimize dopant activation and mitigate the effects of ion implantation.Various sophisticated characterization techniques,including X-ray dif⁃fraction(XRD),Raman spectroscopy,X-ray photoelectron spectroscopy(XPS),and secondary ion mass spec⁃trometry(SIMS)were used to clarify lattice damage.At lower doses,no notable structural alterations were ob⁃served.However,as the dosage increased,specific micro distortions became apparent,which could be attributed to point defects and residual strain.The created lattice damage was recovered by thermal treatment,however,an irreversible strain induced by implantation still existed at heavily dosed samples.
基金Project(2023JJ40040)supported by the Natural Science Foundation of Hunan Province,ChinaProject(502221904)supported by the Project of Innovation-Driven Plan in Central South University,ChinaProject(24C0140)supported by the Scientific Research Fund of Hunan Provincial Education Department,China。
文摘The capacitive performance of carbon materials as supercapacitor electrode is synergistically influenced by the surface porous structure,graphitization structure,and surface atomic doping.However,simple realization of their synergistic regulation still faces significant challenges.Based on the biological porous structure,heteroatom-rich content and low cost of chestnut,this work adopt chestnut as precursor to prepare carbon electrode,of which the pores,graphitization,and surface atomic doping are synergistically regulated by simply changing the activation temperature.The optimized carbon electrode possesses a hierarchical porous structure with partial graphitization and O and N co doping.Benefited from these merits,the chestnut-derived porous carbon as a supercapacitor electrode,can achieve a high specific capacitance of 328.6 F/g at 1 A/g,which still retains 80.8%when the current density enlarging to 20 A/g.By packaging the symmetric electric double-layer capacitor,the device exhibits a specific capacitance of 63.6 F/g at 1 A/g,delivering an energy density of 12.7 W·h/kg at a power density of 600 W/kg.The stability of the device is tested at a current density of 20 A/g,which shows a capacitance retention rate of up to 90%after 10000 charge-discharge cycles.
