Novel graphitic carbon nitride(g-C_(3)N_(4))nanosheet/Bi_(5)O_(7)Br/NH_(2)-MIL-88B(Fe)photocatalysts(denoted as GCN-NSh/Bi_(5)O_(7)Br/FeMOF,in which MOF is metal–organic framework)with double S-scheme heterojunctions...Novel graphitic carbon nitride(g-C_(3)N_(4))nanosheet/Bi_(5)O_(7)Br/NH_(2)-MIL-88B(Fe)photocatalysts(denoted as GCN-NSh/Bi_(5)O_(7)Br/FeMOF,in which MOF is metal–organic framework)with double S-scheme heterojunctions were synthesized by a facile solvothermal route.The resultant materials were examined by X-ray photoelectron spectrometer(XPS),X-ray diffraction(XRD),scanning electron microscopy(SEM),energy dispersive X-ray spectroscopy(EDX),transmission electron microscopy(TEM),high-resolution transmission electron microscopy(HRTEM),photoluminescence spectroscopy(PL),Fourier transform infrared spectroscopy(FT-IR),UV-Vis diffuse reflection spectroscopy(UV-vis DRS),photocurrent density,electrochemical impedance spectroscopy(EIS),and Brunauer–Emmett–Teller(BET)analyses.After the integration of Fe-MOF with GCN-NSh/Bi_(5)O_(7)Br,the removal constant of tetracycline over the optimal GCN-NSh/Bi_(5)O_(7)Br/Fe-MOF(15wt%)nanocomposite was promoted 33 times compared with that of the pristine GCN.The GCN-NSh/Bi_(5)O_(7)Br/Fe-MOF(15wt%)nanocomposite showed superior photoactivity to azithromycin,metronidazole,and cephalexin removal that was 36.4,20.2,and 14.6 times higher than that of pure GCN,respectively.Radical quenching tests showed that·O_(2)-and h+mainly contributed to the elimination reaction.In addition,the nanocomposite maintained excellent activity after 4 successive cycles.Based on the developed n–n heterojunctions among n-GCN-NSh,n-Bi_(5)O_(7)Br,and n-Fe-MOF semiconductors,the double S-scheme charge transfer mechanism was proposed for the destruction of the selected antibiotics.展开更多
Defect and charge transfer efficiency of nano-photocatalysts are important factors which influence their photocatalytic performance.In this work,oxygen vacancies are successfully introduced in the synthesis process of...Defect and charge transfer efficiency of nano-photocatalysts are important factors which influence their photocatalytic performance.In this work,oxygen vacancies are successfully introduced in the synthesis process of Bi_(2)Al_(4)O_(9)/β-Bi_(2)O_(3)heterojunctions through one-step in situ selfcombustion method.High-resolution transmission electron microscopy (HRTEM),UV-Vis diffuse reflectance spectra (UV-Vis DRS),and electron spin resonance (ESR) measurements confirm the existence of oxygen vacancies.In addition,by controlling the ratio of reactants of Bi(NO_(3))_(3)to Al(NO_(3))_(3),the ratio of Bi_(2)Al_(4)O_(9)and β-Bi_(2)O_(3)in the heterojunction can be easily adjusted.Photocurrent responses and surface photovoltage spectroscopy (SPV) indicate that the construction of the Bi_(2)Al_(4)O_(9)/β-Bi_(2)O_(3)heterostructure improves the separation efficiency of the photo-generated electrons and holes.CO_(2)-TPD results imply that the amounts and stability of heterojunctions are enhanced compared with their counterparts.The Bi_(2)Al_(4)O_(9)/β-Bi_(2)O_(3)heterojunction with 14 mol%Bi_(2)Al_(4)O_(9)shows the highest photocatalytic ability for reduction of CO_(2)into CO.The enhanced photoreduction of CO_(2)performance can be ascribed to the synergistic effects of the heterojunction for electron separation and oxygen vacancies for CO_(2)activation.展开更多
Lead halide perovskite (LHP) nanocrystals have been intensely studied as photocatalysts for artificial photosynthesis in recent years.However,the toxicity of lead in LHP seriously limits their potential for widespread...Lead halide perovskite (LHP) nanocrystals have been intensely studied as photocatalysts for artificial photosynthesis in recent years.However,the toxicity of lead in LHP seriously limits their potential for widespread applications.Herein,we first present the synthesis of 2D lead-free halide perovskite (Cs_(3)Bi_(2)I_(9)) nanosheets with self-template-oriented method,in which BiOI/Bi_(2)O_(2) nanosheets were used as the template and Bi ion source simultaneously.Through facile electrostatic self-assembly strategy,a Z-scheme heterojunction composed of Cs_(3)Bi_(2)I_(9)nanosheets and CeO_(2) nanosheets (Cs_(3)Bi_(2)I_(9)/CeO_(2)-3:1) was constructed as photocatalyst for the photo-reduction of CO_(2) coupled with the oxidation of H_(2)O.Due to the matching energy levels and the close interfacial contact between Cs_(3)Bi_(2)I_(9)and CeO_(2) nanosheets,the separation efficiency of the photogenerated carriers in Cs_(3)Bi_(2)I_(9)/CeO_(2)-3:1 composite was significantly improved.Consequently,the environment-friendly halide perovskite heterojunction Cs_(3)Bi_(2)I_(9)/CeO_(2)-3:1presents impressive photocatalytic activity for the reduction of CO_(2)to CH_(4)and CO with an electron consumption yield of 877.04μmol g^(-1),which is over 7 and 15 times higher than those of pristine Cs_(3)Bi_(2)I_(9)and CeO_(2)nanosheets,exceeding the yield of other reported bismuth-based perovskite for photocatalytic CO_(2)reduction.展开更多
Composites of 2D/0D Fe_(2)O_(3)-Bi_(3)TaO_(7)(FO-BTO)prepared by a hydrothermal method in which superfine Bi_(3)TaO_(7) particles were mounted onto lamellae of Fe_(2)O_(3) sheets could efficiently remove aqueous tetra...Composites of 2D/0D Fe_(2)O_(3)-Bi_(3)TaO_(7)(FO-BTO)prepared by a hydrothermal method in which superfine Bi_(3)TaO_(7) particles were mounted onto lamellae of Fe_(2)O_(3) sheets could efficiently remove aqueous tetracycline(TC)residues.The optimal composite FO-3BTO had a TC removal rate of 95%in 120 min under solar light,and its overall properties were better than those of reported photocatalysts.According to XRD,HRTEM,XPS,SEM,PL,EIS,and photocurrent tests,Fe_(2)O_(3) and Bi_(3)TaO_(7) composites formed on effective S-scheme heterojunctions,and the tight contact structure contributed to the increase in efficiency of aqueous TC residue removal.展开更多
The fabrication of efficient catalysts to reduce nitrogen(N_(2))to ammonia(NH3)is a significant challenge for artificial N_(2) fixation under mild conditions.In this work,we demonstrated that the simultaneous introduc...The fabrication of efficient catalysts to reduce nitrogen(N_(2))to ammonia(NH3)is a significant challenge for artificial N_(2) fixation under mild conditions.In this work,we demonstrated that the simultaneous introduction of oxygen vacancies(OVs)and Mo dopants into Bi_(5)O_(7)Br nanosheets can significantly increase the activity for photocatalytic N_(2) fixation.The 1 mol% Mo-doped Bi_(5)O_(7)Br nanosheets exhibited an optimal NH_(3) generation rate of 122.9μmol g^(-1) h^(-1) and durable stability,which is attributed to their optimized conduction band position,suitable absorption edge,large number of light-switchable OVs,and improved charge carrier separation.This work provides a promising approach to design photocatalysts with light-switchable OVs for N_(2) reduction to NH_(3) under mild conditions,highlighting the wide application scope of nanostructured BiOBr-based photocatalysts as effective N_(2) fixation systems.展开更多
At present,the high re-combination rate of photogenerated carriers and the low redox capability of the photocatalyst are two factors that severely limit the improvement of photocatalytic performance.Herein,a dual Z-sc...At present,the high re-combination rate of photogenerated carriers and the low redox capability of the photocatalyst are two factors that severely limit the improvement of photocatalytic performance.Herein,a dual Z-scheme photocatalyst bismuthzirconate/graphitic carbon nitride/silver phosphate (Bi_(2)Zr_(2)O_(7)/g-C_(3)N4/Ag_(3)PO_(4)(BCA)) was synthesized using a co-precipitation method,and a dual Z-scheme heterojunction photocatalytic system was established to decrease the high re-combination rate of photogenerated carriers and consequently improve the photocatalytic performance.The re-combination of electron-hole pairs(e-and h+) in the valence band (VB) of g-C_(3)N4increases the redox potential of e-and h+,leading to significant improvements in the redox capability of the photocatalyst and the efficiency of e--h+separation.As a photosensitizer,Ag_(3)PO_(4)can enhance the visible light absorption capacity of the photocatalyst.The prepared photocatalyst showed strong stability,which was attributed to the efficient suppression of photo-corrosion of Ag_(3)PO_(4)by transferring the e-to the VB of g-C_(3)N4.Tetracycline was degraded efficiently by BCA-10%(the BCA with 10 wt.%of AgPO_(4)) under visible light,and the degradation efficiency was up to 86.2%.This study experimentally suggested that the BCA photocatalyst has broad application prospects in removing antibiotic pollution.展开更多
Rational structure design and regulation are of paramount importance for obtaining electrode materials with desirable electrochemical performance.Here,a novel binder-free electrode with the hollow Co_(9)S_(8) core@mul...Rational structure design and regulation are of paramount importance for obtaining electrode materials with desirable electrochemical performance.Here,a novel binder-free electrode with the hollow Co_(9)S_(8) core@multi-shell structure(CS-x@MXene@Bi_(2)O_(3))derived from metal-organic frameworks(MOFs)precursor is well designed by the electrospinning,sulfuration,carbonization,and hydrothermal processes.In this architecture,the concentration of Co_(9)S_(8)(CS-x)is optimized for an ideal flexible substrate,which alleviates the dimensional variation for long cycle life.The unique cores and the MXene flakes engineered by Bi_(2)O_(3) multiple shells can be responsible for the superior characteristics,including a fast electronic pathway,large specific surface area,enhanced electrical conductivity,and improved electrochemical performance.As expected,the obtained CS-2@MXene@Bi_(2)O_(3) binder-free electrode exhibits a high discharge capacitance of 646.1 F g^(–1)(1 A g^(–1)).Two binder-free electrodes can be assembled into a solid-state supercapacitor with desirable energy and power density,and long-term cyclic stability is demonstrated through 5000 cycles.Given these advantages,the CS-2@MXene@Bi_(2)O_(3) is selected as the electrode in a foldable supercapacitor.More importantly,the specific capacitance is reserved after various deformations.Therefore,it is expected that binder-free electrode materials with the unique core@shell structure design could be applied in wearable and portable energy conversion devices.展开更多
文摘Novel graphitic carbon nitride(g-C_(3)N_(4))nanosheet/Bi_(5)O_(7)Br/NH_(2)-MIL-88B(Fe)photocatalysts(denoted as GCN-NSh/Bi_(5)O_(7)Br/FeMOF,in which MOF is metal–organic framework)with double S-scheme heterojunctions were synthesized by a facile solvothermal route.The resultant materials were examined by X-ray photoelectron spectrometer(XPS),X-ray diffraction(XRD),scanning electron microscopy(SEM),energy dispersive X-ray spectroscopy(EDX),transmission electron microscopy(TEM),high-resolution transmission electron microscopy(HRTEM),photoluminescence spectroscopy(PL),Fourier transform infrared spectroscopy(FT-IR),UV-Vis diffuse reflection spectroscopy(UV-vis DRS),photocurrent density,electrochemical impedance spectroscopy(EIS),and Brunauer–Emmett–Teller(BET)analyses.After the integration of Fe-MOF with GCN-NSh/Bi_(5)O_(7)Br,the removal constant of tetracycline over the optimal GCN-NSh/Bi_(5)O_(7)Br/Fe-MOF(15wt%)nanocomposite was promoted 33 times compared with that of the pristine GCN.The GCN-NSh/Bi_(5)O_(7)Br/Fe-MOF(15wt%)nanocomposite showed superior photoactivity to azithromycin,metronidazole,and cephalexin removal that was 36.4,20.2,and 14.6 times higher than that of pure GCN,respectively.Radical quenching tests showed that·O_(2)-and h+mainly contributed to the elimination reaction.In addition,the nanocomposite maintained excellent activity after 4 successive cycles.Based on the developed n–n heterojunctions among n-GCN-NSh,n-Bi_(5)O_(7)Br,and n-Fe-MOF semiconductors,the double S-scheme charge transfer mechanism was proposed for the destruction of the selected antibiotics.
基金financial support from the National Natural Science Foundation of China(21776059,21376061)the Natural Science Foundation for Distinguished Young Scholars of Hebei Province(B2015208010)the Research Foundation of Hebei Province Education Department(No.ZC2016007)。
文摘Defect and charge transfer efficiency of nano-photocatalysts are important factors which influence their photocatalytic performance.In this work,oxygen vacancies are successfully introduced in the synthesis process of Bi_(2)Al_(4)O_(9)/β-Bi_(2)O_(3)heterojunctions through one-step in situ selfcombustion method.High-resolution transmission electron microscopy (HRTEM),UV-Vis diffuse reflectance spectra (UV-Vis DRS),and electron spin resonance (ESR) measurements confirm the existence of oxygen vacancies.In addition,by controlling the ratio of reactants of Bi(NO_(3))_(3)to Al(NO_(3))_(3),the ratio of Bi_(2)Al_(4)O_(9)and β-Bi_(2)O_(3)in the heterojunction can be easily adjusted.Photocurrent responses and surface photovoltage spectroscopy (SPV) indicate that the construction of the Bi_(2)Al_(4)O_(9)/β-Bi_(2)O_(3)heterostructure improves the separation efficiency of the photo-generated electrons and holes.CO_(2)-TPD results imply that the amounts and stability of heterojunctions are enhanced compared with their counterparts.The Bi_(2)Al_(4)O_(9)/β-Bi_(2)O_(3)heterojunction with 14 mol%Bi_(2)Al_(4)O_(9)shows the highest photocatalytic ability for reduction of CO_(2)into CO.The enhanced photoreduction of CO_(2)performance can be ascribed to the synergistic effects of the heterojunction for electron separation and oxygen vacancies for CO_(2)activation.
基金financially supported by the Natural Science Foundation of Tianjin City (17JCJQJC43800, 19JCQNJC05500)the National Key R&D Program of China (2017YFA0700104)+1 种基金NSFC (21931007)the 111 Project of China (D17003)。
文摘Lead halide perovskite (LHP) nanocrystals have been intensely studied as photocatalysts for artificial photosynthesis in recent years.However,the toxicity of lead in LHP seriously limits their potential for widespread applications.Herein,we first present the synthesis of 2D lead-free halide perovskite (Cs_(3)Bi_(2)I_(9)) nanosheets with self-template-oriented method,in which BiOI/Bi_(2)O_(2) nanosheets were used as the template and Bi ion source simultaneously.Through facile electrostatic self-assembly strategy,a Z-scheme heterojunction composed of Cs_(3)Bi_(2)I_(9)nanosheets and CeO_(2) nanosheets (Cs_(3)Bi_(2)I_(9)/CeO_(2)-3:1) was constructed as photocatalyst for the photo-reduction of CO_(2) coupled with the oxidation of H_(2)O.Due to the matching energy levels and the close interfacial contact between Cs_(3)Bi_(2)I_(9)and CeO_(2) nanosheets,the separation efficiency of the photogenerated carriers in Cs_(3)Bi_(2)I_(9)/CeO_(2)-3:1 composite was significantly improved.Consequently,the environment-friendly halide perovskite heterojunction Cs_(3)Bi_(2)I_(9)/CeO_(2)-3:1presents impressive photocatalytic activity for the reduction of CO_(2)to CH_(4)and CO with an electron consumption yield of 877.04μmol g^(-1),which is over 7 and 15 times higher than those of pristine Cs_(3)Bi_(2)I_(9)and CeO_(2)nanosheets,exceeding the yield of other reported bismuth-based perovskite for photocatalytic CO_(2)reduction.
基金Financial support was provided by the National Natural Science Foundation of China(Grants Nos.51901209,21777078,and 22062016)the Major Project of Inner Mongolia Natural Science Foundation(Grant 2020ZD02)the Project of Research and Development of the Applied Technology for Inner Mongolia(Grant 2020SGG0065).
文摘Composites of 2D/0D Fe_(2)O_(3)-Bi_(3)TaO_(7)(FO-BTO)prepared by a hydrothermal method in which superfine Bi_(3)TaO_(7) particles were mounted onto lamellae of Fe_(2)O_(3) sheets could efficiently remove aqueous tetracycline(TC)residues.The optimal composite FO-3BTO had a TC removal rate of 95%in 120 min under solar light,and its overall properties were better than those of reported photocatalysts.According to XRD,HRTEM,XPS,SEM,PL,EIS,and photocurrent tests,Fe_(2)O_(3) and Bi_(3)TaO_(7) composites formed on effective S-scheme heterojunctions,and the tight contact structure contributed to the increase in efficiency of aqueous TC residue removal.
文摘The fabrication of efficient catalysts to reduce nitrogen(N_(2))to ammonia(NH3)is a significant challenge for artificial N_(2) fixation under mild conditions.In this work,we demonstrated that the simultaneous introduction of oxygen vacancies(OVs)and Mo dopants into Bi_(5)O_(7)Br nanosheets can significantly increase the activity for photocatalytic N_(2) fixation.The 1 mol% Mo-doped Bi_(5)O_(7)Br nanosheets exhibited an optimal NH_(3) generation rate of 122.9μmol g^(-1) h^(-1) and durable stability,which is attributed to their optimized conduction band position,suitable absorption edge,large number of light-switchable OVs,and improved charge carrier separation.This work provides a promising approach to design photocatalysts with light-switchable OVs for N_(2) reduction to NH_(3) under mild conditions,highlighting the wide application scope of nanostructured BiOBr-based photocatalysts as effective N_(2) fixation systems.
基金the financial support provided by the Shandong University Cross Project fund (No.2016JC003)。
文摘At present,the high re-combination rate of photogenerated carriers and the low redox capability of the photocatalyst are two factors that severely limit the improvement of photocatalytic performance.Herein,a dual Z-scheme photocatalyst bismuthzirconate/graphitic carbon nitride/silver phosphate (Bi_(2)Zr_(2)O_(7)/g-C_(3)N4/Ag_(3)PO_(4)(BCA)) was synthesized using a co-precipitation method,and a dual Z-scheme heterojunction photocatalytic system was established to decrease the high re-combination rate of photogenerated carriers and consequently improve the photocatalytic performance.The re-combination of electron-hole pairs(e-and h+) in the valence band (VB) of g-C_(3)N4increases the redox potential of e-and h+,leading to significant improvements in the redox capability of the photocatalyst and the efficiency of e--h+separation.As a photosensitizer,Ag_(3)PO_(4)can enhance the visible light absorption capacity of the photocatalyst.The prepared photocatalyst showed strong stability,which was attributed to the efficient suppression of photo-corrosion of Ag_(3)PO_(4)by transferring the e-to the VB of g-C_(3)N4.Tetracycline was degraded efficiently by BCA-10%(the BCA with 10 wt.%of AgPO_(4)) under visible light,and the degradation efficiency was up to 86.2%.This study experimentally suggested that the BCA photocatalyst has broad application prospects in removing antibiotic pollution.
基金support from the National Natural Science Foundation of China(no.52072307)。
文摘Rational structure design and regulation are of paramount importance for obtaining electrode materials with desirable electrochemical performance.Here,a novel binder-free electrode with the hollow Co_(9)S_(8) core@multi-shell structure(CS-x@MXene@Bi_(2)O_(3))derived from metal-organic frameworks(MOFs)precursor is well designed by the electrospinning,sulfuration,carbonization,and hydrothermal processes.In this architecture,the concentration of Co_(9)S_(8)(CS-x)is optimized for an ideal flexible substrate,which alleviates the dimensional variation for long cycle life.The unique cores and the MXene flakes engineered by Bi_(2)O_(3) multiple shells can be responsible for the superior characteristics,including a fast electronic pathway,large specific surface area,enhanced electrical conductivity,and improved electrochemical performance.As expected,the obtained CS-2@MXene@Bi_(2)O_(3) binder-free electrode exhibits a high discharge capacitance of 646.1 F g^(–1)(1 A g^(–1)).Two binder-free electrodes can be assembled into a solid-state supercapacitor with desirable energy and power density,and long-term cyclic stability is demonstrated through 5000 cycles.Given these advantages,the CS-2@MXene@Bi_(2)O_(3) is selected as the electrode in a foldable supercapacitor.More importantly,the specific capacitance is reserved after various deformations.Therefore,it is expected that binder-free electrode materials with the unique core@shell structure design could be applied in wearable and portable energy conversion devices.
