The photocatalytic conversion of CO_(2)into solar‐powered fuels is viewed as a forward‐looking strategy to address energy scarcity and global warming.This work demonstrated the selective photoreduction of CO_(2)to C...The photocatalytic conversion of CO_(2)into solar‐powered fuels is viewed as a forward‐looking strategy to address energy scarcity and global warming.This work demonstrated the selective photoreduction of CO_(2)to CO using ultrathin Bi_(12)O_(17)Cl_(2)nanosheets decorated with hydrothermally synthesized bismuth clusters and oxygen vacancies(OVs).The characterizations revealed that the coexistences of OVs and Bi clusters generated in situ contributed to the high efficiency of CO_(2)–CO conversion(64.3μmol g^(−1)h^(−1))and perfect selectivity.The OVs on the facet(001)of the ultrathin Bi_(12)O_(17)Cl_(2)nanosheets serve as sites for CO_(2)adsorption and activation sites,capturing photoexcited electrons and prolonging light absorption due to defect states.In addition,the Bi‐cluster generated in situ offers the ability to trap holes and the surface plasmonic resonance effect.This study offers great potential for the construction of semiconductor hybrids as multiphotocatalysts,capable of being used for the elimination and conversion of CO_(2)in terms of energy and environment.展开更多
The insufficient active sites and slow interfacial charge trans-fer of photocatalysts restrict the efficiency of CO_(2) photoreduction.The synchronized modulation of the above key issues is demanding and chal-lenging....The insufficient active sites and slow interfacial charge trans-fer of photocatalysts restrict the efficiency of CO_(2) photoreduction.The synchronized modulation of the above key issues is demanding and chal-lenging.Herein,strain-induced strategy is developed to construct the Bi–O-bonded interface in Cu porphyrin-based monoatomic layer(PML-Cu)and Bi_(12)O_(17)Br_(2)(BOB),which triggers the surface interface dual polarization of PML-Cu/BOB(PBOB).In this multi-step polarization,the built-in electric field formed between the interfaces induces the electron transfer from con-duction band(CB)of BOB to CB of PML-Cu and suppresses its reverse migration.Moreover,the surface polarization of PML-Cu further promotes the electron converge in Cu atoms.The introduction of PML-Cu endows a high density of dispersed Cu active sites on the surface of PBOB,significantly promoting the adsorption and activation of CO_(2) and CO desorption.The conversion rate of CO_(2) photoreduction to CO for PBOB can reach 584.3μmol g-1,which is 7.83 times higher than BOB and 20.01 times than PML-Cu.This work offers valuable insights into multi-step polarization regulation and active site design for catalysts.展开更多
Novel graphene-like boron nitride(BN)/Bi_(3)O_(4)Br photocatalysts have been controllably synthesized through a facile solvothermal method for the first time. Layer contact stacking between graphene-like BN and ultrat...Novel graphene-like boron nitride(BN)/Bi_(3)O_(4)Br photocatalysts have been controllably synthesized through a facile solvothermal method for the first time. Layer contact stacking between graphene-like BN and ultrathin Bi_(3)O_(4)Br was achieved with strong interaction. Dehalogenation is designed to harvest more visible light, and the ultrathin structure of Bi_(3)O_(4)Br is designed to accelerate charge transfer from inside to the surface. After graphene-like BN was engineered, photocatalytic performance greatly improved under visible light irradiation. Graphene-like BN can act as a surface electron-withdrawing center and adsorption center, facilitating molecular oxygen activation. O_(2)^(·-)was determined to be the main active species during the degradation process through analyses of electron spin resonance and XPS valence band spectra.展开更多
Extremely high-temperature and high-pressure requirement of Haber-Bosch process motivates the search for a sustainable ammonia synthesis approach under mild conditions.Photocatalytic technology is a potential solution...Extremely high-temperature and high-pressure requirement of Haber-Bosch process motivates the search for a sustainable ammonia synthesis approach under mild conditions.Photocatalytic technology is a potential solution to convert N2 to ammonia.However,the poor light absorption and low charge carrier separation efficiency in conventional semiconductors are bottlenecks for the application of this technology.Herein,a facile synthesis of anatase TiO_(2)nanosheets with an abundance of surface oxygen vacancies(TiO_(2)-OV)via the calcination treatment was reported.Photocatalytic experiments of the prepared anatase TiO_(2)samples showed that TiO_(2)-OV nanosheets exhibited remarkably increased ammonia yield for solar-driven N2 fixation in pure water,without adding any sacrificial agents.EPR,XPS,XRD,UV-Vis DRS,TEM,Raman,and PL techniques were employed to systematically explore the possible enhanced mechanism.Studies revealed that the introduced surface oxygen vacancies significantly extended the light absorption capability in the visible region,decreased the adsorption and activation barriers of inert N2,and improved the separation and transfer efficiency of the photogenerated electronhole pairs.Thus,a high rate of ammonia evolution in TiO_(2)-OV was realized.This work offers a promising and sustainable approach for the efficient artificial photosynthesis of ammonia.展开更多
Photocatalysis is considered as an ideal strategy for water pollution treatment.However,it remains challenging to design a highly efficient photo-catalytic system through regulating the charge flow via a precise appro...Photocatalysis is considered as an ideal strategy for water pollution treatment.However,it remains challenging to design a highly efficient photo-catalytic system through regulating the charge flow via a precise approach.In this work,a novel NH2-MIL-125(Ti)/Bi2WO6 composite was constructed via self-assembly growing Bi2WO6 nanosheets on NH2-MIL-125(Ti)material.The characterization results demonstrated that NH2-MIL-125(Ti)was successfully incorporated into Bi2WO6 and the photoexcited carriers could be efficiently separated and transferred between the two components.NH2-MIL-125(Ti)/Bi2WO6 composites displayed enhanced photocatalytic activity for the removal of rhodamine B(RhB)and tetracycline(TC)under visible light irradiation,and the optimal weight ratio of NH2-MIL-125(Ti)was determined to be 7 wt%.The introduction of NH2-MIL-125(Ti)into Bi2WO6 could raise the absorption of visible light,accelerate the separation and transfer of charge carriers,and boost photocatalytic activity.This research presents a wide range of possibilities for the further development of novel composites in the field of environment purification.展开更多
The Fe-based ionic liquid doped g-C_3N_4(Fee CN) photocatalyst was firstly prepared base on ultrathin g-C_3N_4 obtained by multiple calcination method with a metal-based reactive ionic liquid [Omim]FeCl_4 for the degr...The Fe-based ionic liquid doped g-C_3N_4(Fee CN) photocatalyst was firstly prepared base on ultrathin g-C_3N_4 obtained by multiple calcination method with a metal-based reactive ionic liquid [Omim]FeCl_4 for the degradation of Rhodamine B(RhB). Experimental results revealed that Fe3+species were doped into the framework of g-C_3N_4. The effect of the amount of Fe-doping on the catalytic activity was performed. The result showed that the Fee CN could effectively degrade RhB under the condition of visible light irradiation. The photocurrent analysis showed that the incorporation of Fe^(3+)into g-C_3N_4 material could accelerate the separation of the photogenerated carriers significantly.At the same time, the reactive species generated during the photodegradation process were tested by radicals trapping experiments and electron spin resonance(ESR). It was proposed that the synergistic effect of■ and ·OH contributed to degrade RhB efficiently.展开更多
Nitrogen and phosphorus co-doped graphene quantum dot-modified Bi5O7 I(NPG/Bi5O7 I)nanorods were fabricated via a simple solvothermal method.The morphology,structure,and optical properties of the as-prepared samples w...Nitrogen and phosphorus co-doped graphene quantum dot-modified Bi5O7 I(NPG/Bi5O7 I)nanorods were fabricated via a simple solvothermal method.The morphology,structure,and optical properties of the as-prepared samples were investigated by X-ray diffraction,scanning electron microscopy,high-resolution transmission electron microscopy,X-ray photoelectron spectroscopy(XPS),and diffused reflectance spectroscopy.The photocatalytic performance was estimated by degrading the broad-spectrum antibiotics tetracycline and enrofloxacin under visible light irradiation.The photodegradation activity of Bi5O7 I improved after its surface was modified with NPGs,which was attributed to an increase in the photogenerated charge transport rate and a decrease in the electron-hole pair recombination efficiency.From the electron spin resonance spectra,XPS valence band data,and free radical trapping experiment results,the main active substances involved in the photocatalytic degradation process were determined to be photogenerated holes and superoxide radicals.A possible photocatalytic degradation mechanism for NPG/Bi5O7 I nanorods was proposed.展开更多
The oxygen reduction reaction(ORR)is a vitally important process in fuel cells.The development of high‐performance and low‐cost ORR electrocatalysts with outstanding stability is essential for the commercialization ...The oxygen reduction reaction(ORR)is a vitally important process in fuel cells.The development of high‐performance and low‐cost ORR electrocatalysts with outstanding stability is essential for the commercialization of the electrochemical energy technology.Herein,we report a facile synthesis of cobalt(Co)and nitrogen(N)co‐doped carbon nanotube@porous carbon(Co/N/CNT@PC‐800)electrocatalyst through a one‐step pyrolysis of waste paper,dicyandiamide,and cobalt(II)acetylacetonate.The surface of the hierarchical porous carbon supported a large number of carbon nanotubes(CNTs),which were derived from dicyandiamide through the catalysis of Co.The addition of Co resulted in the formation of a hierarchical micro/mesoporous structure,which was beneficial for the exposure of active sites and rapid transportation of ORR‐relevant species(O2,H+,OH?,and H2O).The doped N and Co formed more active sites to enhance the ORR activity of the electrocatalyst.The Co/N/CNT@PC‐800 material exhibited optimal ORR performance with an onset potential of 0.005 V vs.Ag/AgCl and a half‐wave potential of?0.173 V vs.Ag/AgCl.Meanwhile,the electrocatalyst showed an excellent methanol tolerance and a long‐term operational durability than that of Pt/C,as well as a quasi‐four‐electron reaction pathway.The low‐cost and simple synthesis approach makes the Co/N/CNT@PC‐800 a prospective electrocatalyst for the ORR.Furthermore,this work provides an alternative approach for exploring the use of biomass‐derived electrocatalysts for renewable energy applications.展开更多
In this work, two kinds of self-assembled hierarchical BiOBr microcrystals were rapidly synthesized through a simple microwave-assisted route in the presence of reactable ionic liquid 1-hexadecyl-3-methylimidazolium b...In this work, two kinds of self-assembled hierarchical BiOBr microcrystals were rapidly synthesized through a simple microwave-assisted route in the presence of reactable ionic liquid 1-hexadecyl-3-methylimidazolium bromide([C_(16)mim]Br). These porous and hollow BiOBr microspheres were obtained via a facile solvothermal method with or without polyvinyl pyrrolidone(PVP), respectively. During the synthetic process, ionic liquid [C_(16)mim]Br played as solvent, reactant and template at the same time. Moreover, the BiOBr hollow and porous microspheres exhibited outstanding photocatalytic activities for the degradation of rhodamine B(RhB) under visible light irradiation. A possible photocatalytic mechanism was also discussed in detail. It can be assumed that the higher photocatalytic activities of BiOBr porous microspheres materials could be ascribed to the novel structure, larger specific surface area, narrower band gap structure and smaller particle size.展开更多
Mesoporous FeVO4 nanorods were successfully synthesized by calcining the precursor Fe- VO4·1.1H2O nanorods, which were obtained via a simple hydrothermal method in the presence of a reactable metal-ion-containing...Mesoporous FeVO4 nanorods were successfully synthesized by calcining the precursor Fe- VO4·1.1H2O nanorods, which were obtained via a simple hydrothermal method in the presence of a reactable metal-ion-containing ionic liquid, 1-octyl-3-methylimidazolium tetrachloride ferrate(III)([Omim]FeCl4). The structure and morphology of the prepared samples were examined using various characterization techniques. During the synthetic process,[Omim]FeCl4 acted as the solvent, reactant, and capping agent simultaneously. Moreover, the porous FeVO4 nanorods as the heterogeneous photo-Fenton-like semiconductor catalyst for the degradation of tetracycline and rhodamine B under visible light irradiation exhibited excellent photocatalytic activity. This excellent photocatalytic activity of the porous FeVO4 nanorods can be attributed to the synergistic effect of their high electron-hole pair separation rate, suitable band gap structure, and large specific surface area. The possible photocatalytic degradation mechanism of FeVO4/H2O2 photocatalytic systems was also discussed in detail.展开更多
The sluggish electrochemical oxygen evolution reaction(OER) is a crucial process for clean energy conversion technology.The preparation of non-precious electrocatalysts with high performance for OER is still a main ch...The sluggish electrochemical oxygen evolution reaction(OER) is a crucial process for clean energy conversion technology.The preparation of non-precious electrocatalysts with high performance for OER is still a main challenge.Herein,we report a FeNi_(3) nanoparticles incorporated on N-doped hollow carbon rod with extraordinary performance toward OER by in situ annealing the Ni-doped Fe based metal-organic frameworks(MOFs) precursors.Meanwhile,the pristine N atoms of MOFs doped into carbon frameworks can enhance the electrical conductivity,boost electron mass transport and electron transfer,and construct more active sites.Furthermore,constructing the Fe-Ni alloy structure can facilitate the formation of O-O bond,optimize the free energy for intermediate adsorption and improve OER performance.The as-prepared Fe-Ni bimetal decorated hollow N-doped nanocarbon hybrid structure possesses superior OER performance,which is surpass commercial IrO_(2) at a overpotential of only 340 mV to achieve the current density of 10 mA cm^(-2),as well as a small Tafel slope of 86.67 mV dec^(-1) in alkaline electrolyte.The Fe-Ni alloy/hollow N-doped nanocarbon hybrid structure shining the bright future for obtaining earth-abundant and superior efficient anode OER electrocatalyst.展开更多
Although CO_(2)photoreduction is a promising method for solar‐to‐fuel conversion,it suffers from low charge transfer efficiency of the photocatalysts.To improve the CO_(2)photoreduction performance,introduction of e...Although CO_(2)photoreduction is a promising method for solar‐to‐fuel conversion,it suffers from low charge transfer efficiency of the photocatalysts.To improve the CO_(2)photoreduction performance,introduction of electron‐accumulated materials on the photocatalyst surface is considered an effective method.In this study,the Bi_(19)S_(27)Br_(3)/BiOBr composites were designed and synthesized.The Bi19S27Br3 nanorod in this photocatalytic system acts as an electron‐accumulated active site for extracting the photogenerated electrons on the BiOBr surface and for effectively activating the CO2 molecules.As a result,Bi_(19)S_(27)Br_(3)/BiOBr composites exhibit the higher charge carrier transfer efficiency and further improves the CO_(2)photoreduction performance relative to that of pure Bi_(19)S_(27)Br_(3)and BiOBr.The rate of CO formation using Bi_(19)S_(27)Br_(3)/BiOBr‐5 is about 8.74 and 2.40 times that using Bi_(19)S_(27)Br_(3)and BiOBr,respectively.This work provides new insights for the application of Bi_(19)S_(27)Br_(3)as an electron‐accumulating site for achieving high photocatalytic CO2 reduction performance in the future.展开更多
Increasing the utilization efficiency of photogenerated electrons is highly recognized as one of the ef-ficient approaches to boost the photocatalytic CO_(2)conversion efficiency.Herein,ZIF-67-derived porous carbon(PC...Increasing the utilization efficiency of photogenerated electrons is highly recognized as one of the ef-ficient approaches to boost the photocatalytic CO_(2)conversion efficiency.Herein,ZIF-67-derived porous carbon(PC)material was employed for the construction of PC@ultrafine Bi_(12)O_(17)Br_(2)nanotubes(PC@BOB NTs)composites through a facile solvothermal synthesis in order to optimize the use of excited elec-trons in the BOB NTs.Photoelectrochemical characterization results revealed that the introduction of PC material achieved a faster charge separation rate in the PC@BOB composites,ensuring more photogener-ated electrons participate in the CO_(2)adsorption and activation process.Moreover,the pore structures of ZIF-67-derived PC material provided abundant confined spaces for the enrichment of CO_(2)molecules.Af-ter 5 h of Xenon lamp irradiation,PC@BOB composites exhibited obviously increased photocatalytic CO_(2)reduction activity in the pure water.When the addition amount of PC was 5 wt%,the PC@BOB-2 com-posite showed the highest CO evolution rate of 359.70μmol/g,which was 2.95 times higher than that of the pure BOB NTs.This work provides some independent insights into the applications of Metal-Organic Framework(MOF)-derived hierarchical porous structures to strengthen the CO_(2)enrichment,as well as the excited charge utilization efficiency,thus achieving a high solar-to-fuel conversion efficiency.展开更多
Artificial photosynthesis of valuable chemicals from CO_(2)is a potential way to achieve sustainable carbon cycle.The CO_(2)conversion activity is still inhibited by the sluggish charge kinetics and poor CO_(2)activat...Artificial photosynthesis of valuable chemicals from CO_(2)is a potential way to achieve sustainable carbon cycle.The CO_(2)conversion activity is still inhibited by the sluggish charge kinetics and poor CO_(2)activation.Herein,Ag nanoparticles coupled Bi OBr have been constructed by in-situ photoreduction strategy.The crafting of interface between Ag nanoparticles and Bi OBr nanosheets,achieving an ultra-fast charge transfer.The Bi OBr semiconductor excited electrons and plasmonic Ag nanoparticles generated high-energy hot electrons synchronous accelerates the C=O double bond activation.Thus,the optimized Ag/BiOBr-2 heterostructure shows excellent CO_(2)photoreduction activity with CO production of 133.75 and 6.83μmol/g under 5 h of 300 W Xe lamp and visible light(λ>400 nm)irradiation,which is 1.51 and 2.81 folds versus the pristine Bi OBr,respectively.The mechanism of CO_(2)photoreduction was in-depth understood through in-situ FT-IR spectrum and density functional theory calculations.This study provides some new perspectives into efficient photocatalytic CO_(2)reduction.展开更多
Defect engineering has been demonstrated to be an appealing strategy to boost the photocatalytic activity of materials.However,can higher defect concentration bring about higher photocatalytic activity?This is an open...Defect engineering has been demonstrated to be an appealing strategy to boost the photocatalytic activity of materials.However,can higher defect concentration bring about higher photocatalytic activity?This is an open question.In this work,BiPO_(4)photocatalysts with controllable oxygen vacancy concentrations were successfully synthesized.The photocatalytic activity of the obtained BiPO_(4)photocatalysts was determined by the removal of ciprofloxacin and 4-chlorophenol,as well as CO_(2)photoreduction.The BiPO4materials with lower oxygen vacancy concentration could display unexpected higher photocatalytic efficiency.Through the investigation of different factors which may affect the photocatalytic performance,such as crystal structure,morphology,specific surface area,defect,and energy band structure,it can be found that the energy band structure difference was responsible for the enhanced photocatalytic activity.展开更多
Novel carbon quantum dots（CQDs）/Bi OBr composite photocatalysts have been constructed through a facile hydrothermal synthesis in the presence of ionic liquid 1-hexadecyl-3-methylimidazolium bromide（[C16 mim]Br）. S...Novel carbon quantum dots（CQDs）/Bi OBr composite photocatalysts have been constructed through a facile hydrothermal synthesis in the presence of ionic liquid 1-hexadecyl-3-methylimidazolium bromide（[C16 mim]Br）. Series of characterizations have been performed to confirm the uniform distribution of CQDs in Bi OBr nanosheets and the synergistic effect for photocatalytic degradation organic pollutants between CQDs and Bi OBr. The results show that 3.1 wt% CQDs/Bi OBr photocatalyst possesses the best photocatalytic activity for the degradation of colorless antibiotic tetracycline（TC）, endocrine disrupter bisphenol A（BPA） and dye rhodamine B（Rh B）, under visible light irradiation, which exhibited the highest photocatalytic performance. The enhanced photocatalytic performance for CQDs/Bi OBr composites could be attributed to the wider optical absorption range and fast separation of photogenerated charge carriers after the introduction of CQDs. The key roles of CQDs for the enhanced photocatalytic activity of Bi OBr have been discussed. A possible mechanism of CQDs/Bi OBr on the enhancement of visible light performance was proposed.展开更多
Integrating semiconductor photocatalysts with outstanding visible light absorption and fast surface/interface charge transfer kinetics is still an enormous challenge for efficient CO_(2)photoreduction.In this work,the...Integrating semiconductor photocatalysts with outstanding visible light absorption and fast surface/interface charge transfer kinetics is still an enormous challenge for efficient CO_(2)photoreduction.In this work,the Au nanoparticles have been coupled with ultrathin BiOBr nanosheets,the formed heterostructure(Au/BiOBr)pos-sesses a localized surface plasmon resonance(LSPR)and enhances the visible light absorption ability,as well as forms a fast charge transport channel on the interface between Au and BiOBr.Thus,the heterostructure photo-catalyst exhibits higher photocatalytic CO_(2)to CO performance(135.3/16.43μmol g^(-1))than that of BiOBr(89.0/6.46μmol g^(-1))under 300 W Xe lamp and visible light(λ>400 nm)irradiation for 5 h,respectively.Finally,the in situ FT-IR spectroscopy revealed CO_(2)photoreduction process and found that the*COOH is the key intermediate for CO_(2)to CO.This work provides an effective method to construct multielectron transfer scheme for efficient photocatalytic CO_(2)reduction.展开更多
基金Natural Science Foundation of Shandong Province,Grant/Award Number:ZR2022MB106national training program of innovation and entrepreneurship for undergraduates,Grant/Award Number:202210424099National Natural Science Foundation of China,Grant/Award Numbers:21601067,21701057,21905147。
文摘The photocatalytic conversion of CO_(2)into solar‐powered fuels is viewed as a forward‐looking strategy to address energy scarcity and global warming.This work demonstrated the selective photoreduction of CO_(2)to CO using ultrathin Bi_(12)O_(17)Cl_(2)nanosheets decorated with hydrothermally synthesized bismuth clusters and oxygen vacancies(OVs).The characterizations revealed that the coexistences of OVs and Bi clusters generated in situ contributed to the high efficiency of CO_(2)–CO conversion(64.3μmol g^(−1)h^(−1))and perfect selectivity.The OVs on the facet(001)of the ultrathin Bi_(12)O_(17)Cl_(2)nanosheets serve as sites for CO_(2)adsorption and activation sites,capturing photoexcited electrons and prolonging light absorption due to defect states.In addition,the Bi‐cluster generated in situ offers the ability to trap holes and the surface plasmonic resonance effect.This study offers great potential for the construction of semiconductor hybrids as multiphotocatalysts,capable of being used for the elimination and conversion of CO_(2)in terms of energy and environment.
基金This work was supported by the National Natural Science Foundation of China(Nos.22138011,22205108,22378206)Open Research Fund of Key Laboratory of the Ministry of Education for Advanced Catalysis Materials and Zhejiang Key Laboratory for Reactive Chemistry on Solid Surfaces(KLMEACM 202201),Zhejiang Normal University.
文摘The insufficient active sites and slow interfacial charge trans-fer of photocatalysts restrict the efficiency of CO_(2) photoreduction.The synchronized modulation of the above key issues is demanding and chal-lenging.Herein,strain-induced strategy is developed to construct the Bi–O-bonded interface in Cu porphyrin-based monoatomic layer(PML-Cu)and Bi_(12)O_(17)Br_(2)(BOB),which triggers the surface interface dual polarization of PML-Cu/BOB(PBOB).In this multi-step polarization,the built-in electric field formed between the interfaces induces the electron transfer from con-duction band(CB)of BOB to CB of PML-Cu and suppresses its reverse migration.Moreover,the surface polarization of PML-Cu further promotes the electron converge in Cu atoms.The introduction of PML-Cu endows a high density of dispersed Cu active sites on the surface of PBOB,significantly promoting the adsorption and activation of CO_(2) and CO desorption.The conversion rate of CO_(2) photoreduction to CO for PBOB can reach 584.3μmol g-1,which is 7.83 times higher than BOB and 20.01 times than PML-Cu.This work offers valuable insights into multi-step polarization regulation and active site design for catalysts.
基金financially supported by the Fundamental Research Funds for the Central Universities (No.30922010302)the Start-Up Grant from Nanjing University of Science and Technology (AE89991/397)。
文摘Novel graphene-like boron nitride(BN)/Bi_(3)O_(4)Br photocatalysts have been controllably synthesized through a facile solvothermal method for the first time. Layer contact stacking between graphene-like BN and ultrathin Bi_(3)O_(4)Br was achieved with strong interaction. Dehalogenation is designed to harvest more visible light, and the ultrathin structure of Bi_(3)O_(4)Br is designed to accelerate charge transfer from inside to the surface. After graphene-like BN was engineered, photocatalytic performance greatly improved under visible light irradiation. Graphene-like BN can act as a surface electron-withdrawing center and adsorption center, facilitating molecular oxygen activation. O_(2)^(·-)was determined to be the main active species during the degradation process through analyses of electron spin resonance and XPS valence band spectra.
基金supported by the National Natural Science Foundation of China(No.22108108,22205108,and No.22108106)China Postdoctoral Science Foundation No.2022M721381.
文摘Extremely high-temperature and high-pressure requirement of Haber-Bosch process motivates the search for a sustainable ammonia synthesis approach under mild conditions.Photocatalytic technology is a potential solution to convert N2 to ammonia.However,the poor light absorption and low charge carrier separation efficiency in conventional semiconductors are bottlenecks for the application of this technology.Herein,a facile synthesis of anatase TiO_(2)nanosheets with an abundance of surface oxygen vacancies(TiO_(2)-OV)via the calcination treatment was reported.Photocatalytic experiments of the prepared anatase TiO_(2)samples showed that TiO_(2)-OV nanosheets exhibited remarkably increased ammonia yield for solar-driven N2 fixation in pure water,without adding any sacrificial agents.EPR,XPS,XRD,UV-Vis DRS,TEM,Raman,and PL techniques were employed to systematically explore the possible enhanced mechanism.Studies revealed that the introduced surface oxygen vacancies significantly extended the light absorption capability in the visible region,decreased the adsorption and activation barriers of inert N2,and improved the separation and transfer efficiency of the photogenerated electronhole pairs.Thus,a high rate of ammonia evolution in TiO_(2)-OV was realized.This work offers a promising and sustainable approach for the efficient artificial photosynthesis of ammonia.
基金This work was financially supported by the National Natural Science Foundation of China(Nos.21476098,21471069 and 21576123)and Jiangsu University Scientific Research Funding(No.11JDG0146).
文摘Photocatalysis is considered as an ideal strategy for water pollution treatment.However,it remains challenging to design a highly efficient photo-catalytic system through regulating the charge flow via a precise approach.In this work,a novel NH2-MIL-125(Ti)/Bi2WO6 composite was constructed via self-assembly growing Bi2WO6 nanosheets on NH2-MIL-125(Ti)material.The characterization results demonstrated that NH2-MIL-125(Ti)was successfully incorporated into Bi2WO6 and the photoexcited carriers could be efficiently separated and transferred between the two components.NH2-MIL-125(Ti)/Bi2WO6 composites displayed enhanced photocatalytic activity for the removal of rhodamine B(RhB)and tetracycline(TC)under visible light irradiation,and the optimal weight ratio of NH2-MIL-125(Ti)was determined to be 7 wt%.The introduction of NH2-MIL-125(Ti)into Bi2WO6 could raise the absorption of visible light,accelerate the separation and transfer of charge carriers,and boost photocatalytic activity.This research presents a wide range of possibilities for the further development of novel composites in the field of environment purification.
基金the financial support from the National Natural Science Foundation of China(No.21722604,21576122)Chinese Postdoctoral Science Foundation(No.2017M611726)
文摘The Fe-based ionic liquid doped g-C_3N_4(Fee CN) photocatalyst was firstly prepared base on ultrathin g-C_3N_4 obtained by multiple calcination method with a metal-based reactive ionic liquid [Omim]FeCl_4 for the degradation of Rhodamine B(RhB). Experimental results revealed that Fe3+species were doped into the framework of g-C_3N_4. The effect of the amount of Fe-doping on the catalytic activity was performed. The result showed that the Fee CN could effectively degrade RhB under the condition of visible light irradiation. The photocurrent analysis showed that the incorporation of Fe^(3+)into g-C_3N_4 material could accelerate the separation of the photogenerated carriers significantly.At the same time, the reactive species generated during the photodegradation process were tested by radicals trapping experiments and electron spin resonance(ESR). It was proposed that the synergistic effect of■ and ·OH contributed to degrade RhB efficiently.
文摘Nitrogen and phosphorus co-doped graphene quantum dot-modified Bi5O7 I(NPG/Bi5O7 I)nanorods were fabricated via a simple solvothermal method.The morphology,structure,and optical properties of the as-prepared samples were investigated by X-ray diffraction,scanning electron microscopy,high-resolution transmission electron microscopy,X-ray photoelectron spectroscopy(XPS),and diffused reflectance spectroscopy.The photocatalytic performance was estimated by degrading the broad-spectrum antibiotics tetracycline and enrofloxacin under visible light irradiation.The photodegradation activity of Bi5O7 I improved after its surface was modified with NPGs,which was attributed to an increase in the photogenerated charge transport rate and a decrease in the electron-hole pair recombination efficiency.From the electron spin resonance spectra,XPS valence band data,and free radical trapping experiment results,the main active substances involved in the photocatalytic degradation process were determined to be photogenerated holes and superoxide radicals.A possible photocatalytic degradation mechanism for NPG/Bi5O7 I nanorods was proposed.
基金supported by the National Nature Science Foundation of China(21476098,21471069,21576123)International Postdoctoral Exchange Fellowship Program of China Postdoctoral Council(20150060)~~
文摘The oxygen reduction reaction(ORR)is a vitally important process in fuel cells.The development of high‐performance and low‐cost ORR electrocatalysts with outstanding stability is essential for the commercialization of the electrochemical energy technology.Herein,we report a facile synthesis of cobalt(Co)and nitrogen(N)co‐doped carbon nanotube@porous carbon(Co/N/CNT@PC‐800)electrocatalyst through a one‐step pyrolysis of waste paper,dicyandiamide,and cobalt(II)acetylacetonate.The surface of the hierarchical porous carbon supported a large number of carbon nanotubes(CNTs),which were derived from dicyandiamide through the catalysis of Co.The addition of Co resulted in the formation of a hierarchical micro/mesoporous structure,which was beneficial for the exposure of active sites and rapid transportation of ORR‐relevant species(O2,H+,OH?,and H2O).The doped N and Co formed more active sites to enhance the ORR activity of the electrocatalyst.The Co/N/CNT@PC‐800 material exhibited optimal ORR performance with an onset potential of 0.005 V vs.Ag/AgCl and a half‐wave potential of?0.173 V vs.Ag/AgCl.Meanwhile,the electrocatalyst showed an excellent methanol tolerance and a long‐term operational durability than that of Pt/C,as well as a quasi‐four‐electron reaction pathway.The low‐cost and simple synthesis approach makes the Co/N/CNT@PC‐800 a prospective electrocatalyst for the ORR.Furthermore,this work provides an alternative approach for exploring the use of biomass‐derived electrocatalysts for renewable energy applications.
基金financially supported by the National Natural Science Foundation of China (No. 21476098,21471069 and 21576123)the Doctoral Innovation Fund of Jiangsu Province (KYZZ16_0340)+1 种基金the Science and Technology support program of Zhenjiang (SH2014018)the Natural Science Foundation of Jiangsu Province (BK2012717)
文摘In this work, two kinds of self-assembled hierarchical BiOBr microcrystals were rapidly synthesized through a simple microwave-assisted route in the presence of reactable ionic liquid 1-hexadecyl-3-methylimidazolium bromide([C_(16)mim]Br). These porous and hollow BiOBr microspheres were obtained via a facile solvothermal method with or without polyvinyl pyrrolidone(PVP), respectively. During the synthetic process, ionic liquid [C_(16)mim]Br played as solvent, reactant and template at the same time. Moreover, the BiOBr hollow and porous microspheres exhibited outstanding photocatalytic activities for the degradation of rhodamine B(RhB) under visible light irradiation. A possible photocatalytic mechanism was also discussed in detail. It can be assumed that the higher photocatalytic activities of BiOBr porous microspheres materials could be ascribed to the novel structure, larger specific surface area, narrower band gap structure and smaller particle size.
基金financially supported by the National Natural Science Foundation of China(21471069,21476098,and 21576123)Jiangsu University Scientific Research Funding(11JDG0146)~~
文摘Mesoporous FeVO4 nanorods were successfully synthesized by calcining the precursor Fe- VO4·1.1H2O nanorods, which were obtained via a simple hydrothermal method in the presence of a reactable metal-ion-containing ionic liquid, 1-octyl-3-methylimidazolium tetrachloride ferrate(III)([Omim]FeCl4). The structure and morphology of the prepared samples were examined using various characterization techniques. During the synthetic process,[Omim]FeCl4 acted as the solvent, reactant, and capping agent simultaneously. Moreover, the porous FeVO4 nanorods as the heterogeneous photo-Fenton-like semiconductor catalyst for the degradation of tetracycline and rhodamine B under visible light irradiation exhibited excellent photocatalytic activity. This excellent photocatalytic activity of the porous FeVO4 nanorods can be attributed to the synergistic effect of their high electron-hole pair separation rate, suitable band gap structure, and large specific surface area. The possible photocatalytic degradation mechanism of FeVO4/H2O2 photocatalytic systems was also discussed in detail.
基金financially supported by the National Natural Science Foundation of China (Nos. 21576123 and 21878134)Jiangsu University Scientific Research Funding (No. 11JDG0146)。
文摘The sluggish electrochemical oxygen evolution reaction(OER) is a crucial process for clean energy conversion technology.The preparation of non-precious electrocatalysts with high performance for OER is still a main challenge.Herein,we report a FeNi_(3) nanoparticles incorporated on N-doped hollow carbon rod with extraordinary performance toward OER by in situ annealing the Ni-doped Fe based metal-organic frameworks(MOFs) precursors.Meanwhile,the pristine N atoms of MOFs doped into carbon frameworks can enhance the electrical conductivity,boost electron mass transport and electron transfer,and construct more active sites.Furthermore,constructing the Fe-Ni alloy structure can facilitate the formation of O-O bond,optimize the free energy for intermediate adsorption and improve OER performance.The as-prepared Fe-Ni bimetal decorated hollow N-doped nanocarbon hybrid structure possesses superior OER performance,which is surpass commercial IrO_(2) at a overpotential of only 340 mV to achieve the current density of 10 mA cm^(-2),as well as a small Tafel slope of 86.67 mV dec^(-1) in alkaline electrolyte.The Fe-Ni alloy/hollow N-doped nanocarbon hybrid structure shining the bright future for obtaining earth-abundant and superior efficient anode OER electrocatalyst.
文摘Although CO_(2)photoreduction is a promising method for solar‐to‐fuel conversion,it suffers from low charge transfer efficiency of the photocatalysts.To improve the CO_(2)photoreduction performance,introduction of electron‐accumulated materials on the photocatalyst surface is considered an effective method.In this study,the Bi_(19)S_(27)Br_(3)/BiOBr composites were designed and synthesized.The Bi19S27Br3 nanorod in this photocatalytic system acts as an electron‐accumulated active site for extracting the photogenerated electrons on the BiOBr surface and for effectively activating the CO2 molecules.As a result,Bi_(19)S_(27)Br_(3)/BiOBr composites exhibit the higher charge carrier transfer efficiency and further improves the CO_(2)photoreduction performance relative to that of pure Bi_(19)S_(27)Br_(3)and BiOBr.The rate of CO formation using Bi_(19)S_(27)Br_(3)/BiOBr‐5 is about 8.74 and 2.40 times that using Bi_(19)S_(27)Br_(3)and BiOBr,respectively.This work provides new insights for the application of Bi_(19)S_(27)Br_(3)as an electron‐accumulating site for achieving high photocatalytic CO2 reduction performance in the future.
基金supported by the National Natural Science Foundation of China(Nos.22108108,22108106,22109055)China Postdoctoral Science Foundation(No.2022M721381).
文摘Increasing the utilization efficiency of photogenerated electrons is highly recognized as one of the ef-ficient approaches to boost the photocatalytic CO_(2)conversion efficiency.Herein,ZIF-67-derived porous carbon(PC)material was employed for the construction of PC@ultrafine Bi_(12)O_(17)Br_(2)nanotubes(PC@BOB NTs)composites through a facile solvothermal synthesis in order to optimize the use of excited elec-trons in the BOB NTs.Photoelectrochemical characterization results revealed that the introduction of PC material achieved a faster charge separation rate in the PC@BOB composites,ensuring more photogener-ated electrons participate in the CO_(2)adsorption and activation process.Moreover,the pore structures of ZIF-67-derived PC material provided abundant confined spaces for the enrichment of CO_(2)molecules.Af-ter 5 h of Xenon lamp irradiation,PC@BOB composites exhibited obviously increased photocatalytic CO_(2)reduction activity in the pure water.When the addition amount of PC was 5 wt%,the PC@BOB-2 com-posite showed the highest CO evolution rate of 359.70μmol/g,which was 2.95 times higher than that of the pure BOB NTs.This work provides some independent insights into the applications of Metal-Organic Framework(MOF)-derived hierarchical porous structures to strengthen the CO_(2)enrichment,as well as the excited charge utilization efficiency,thus achieving a high solar-to-fuel conversion efficiency.
基金financially supported by the National Natural Science Foundation of China(Nos.22108106,21878134,21576123)China Postdoctoral Science Foundation(No.2020M680065)+1 种基金Hong Kong Scholar Program(No.XJ2021021)Key Laboratory of Electrochemical Energy Storage and Energy Conversion of Hainan Province(No.KFKT2021005)。
文摘Artificial photosynthesis of valuable chemicals from CO_(2)is a potential way to achieve sustainable carbon cycle.The CO_(2)conversion activity is still inhibited by the sluggish charge kinetics and poor CO_(2)activation.Herein,Ag nanoparticles coupled Bi OBr have been constructed by in-situ photoreduction strategy.The crafting of interface between Ag nanoparticles and Bi OBr nanosheets,achieving an ultra-fast charge transfer.The Bi OBr semiconductor excited electrons and plasmonic Ag nanoparticles generated high-energy hot electrons synchronous accelerates the C=O double bond activation.Thus,the optimized Ag/BiOBr-2 heterostructure shows excellent CO_(2)photoreduction activity with CO production of 133.75 and 6.83μmol/g under 5 h of 300 W Xe lamp and visible light(λ>400 nm)irradiation,which is 1.51 and 2.81 folds versus the pristine Bi OBr,respectively.The mechanism of CO_(2)photoreduction was in-depth understood through in-situ FT-IR spectrum and density functional theory calculations.This study provides some new perspectives into efficient photocatalytic CO_(2)reduction.
基金financially supported by the National Natural Science Foundation of China(No.22002014)the Funding for scientific research startup of Jiangsu University(No.20JDG15)+1 种基金Fundamental Research Funds for the Central Universities(No.30922010302)Start-Up Grant(No.AE89991/397)from Nanjing University of Science and Technology。
文摘Defect engineering has been demonstrated to be an appealing strategy to boost the photocatalytic activity of materials.However,can higher defect concentration bring about higher photocatalytic activity?This is an open question.In this work,BiPO_(4)photocatalysts with controllable oxygen vacancy concentrations were successfully synthesized.The photocatalytic activity of the obtained BiPO_(4)photocatalysts was determined by the removal of ciprofloxacin and 4-chlorophenol,as well as CO_(2)photoreduction.The BiPO4materials with lower oxygen vacancy concentration could display unexpected higher photocatalytic efficiency.Through the investigation of different factors which may affect the photocatalytic performance,such as crystal structure,morphology,specific surface area,defect,and energy band structure,it can be found that the energy band structure difference was responsible for the enhanced photocatalytic activity.
基金financially supported by the National Natural Science Foundation of China (Nos. 21471069, 21476098 and 21576123)Jiangsu University Scientific Research Funding (No. 11JDG0146)Doctoral Innovation Fund of Jiangsu Province (No. KYCX17_1791)
文摘Novel carbon quantum dots（CQDs）/Bi OBr composite photocatalysts have been constructed through a facile hydrothermal synthesis in the presence of ionic liquid 1-hexadecyl-3-methylimidazolium bromide（[C16 mim]Br）. Series of characterizations have been performed to confirm the uniform distribution of CQDs in Bi OBr nanosheets and the synergistic effect for photocatalytic degradation organic pollutants between CQDs and Bi OBr. The results show that 3.1 wt% CQDs/Bi OBr photocatalyst possesses the best photocatalytic activity for the degradation of colorless antibiotic tetracycline（TC）, endocrine disrupter bisphenol A（BPA） and dye rhodamine B（Rh B）, under visible light irradiation, which exhibited the highest photocatalytic performance. The enhanced photocatalytic performance for CQDs/Bi OBr composites could be attributed to the wider optical absorption range and fast separation of photogenerated charge carriers after the introduction of CQDs. The key roles of CQDs for the enhanced photocatalytic activity of Bi OBr have been discussed. A possible mechanism of CQDs/Bi OBr on the enhancement of visible light performance was proposed.
基金This work was financially supported by the National Natural Science Foundation of China(Nos.21878134,21576123)China Postdoctoral Science Foundation(No.2020M680065).
文摘Integrating semiconductor photocatalysts with outstanding visible light absorption and fast surface/interface charge transfer kinetics is still an enormous challenge for efficient CO_(2)photoreduction.In this work,the Au nanoparticles have been coupled with ultrathin BiOBr nanosheets,the formed heterostructure(Au/BiOBr)pos-sesses a localized surface plasmon resonance(LSPR)and enhances the visible light absorption ability,as well as forms a fast charge transport channel on the interface between Au and BiOBr.Thus,the heterostructure photo-catalyst exhibits higher photocatalytic CO_(2)to CO performance(135.3/16.43μmol g^(-1))than that of BiOBr(89.0/6.46μmol g^(-1))under 300 W Xe lamp and visible light(λ>400 nm)irradiation for 5 h,respectively.Finally,the in situ FT-IR spectroscopy revealed CO_(2)photoreduction process and found that the*COOH is the key intermediate for CO_(2)to CO.This work provides an effective method to construct multielectron transfer scheme for efficient photocatalytic CO_(2)reduction.
