Emerging contaminants in water sources present serious environmental and health risks,creating an urgent need for efficient and reliable treatment strategies.Photocatalytic advanced oxidation processes(AOPs)provide ra...Emerging contaminants in water sources present serious environmental and health risks,creating an urgent need for efficient and reliable treatment strategies.Photocatalytic advanced oxidation processes(AOPs)provide rapid reaction rates and strong oxidation capabilities,however,comprehensive evaluations of wastewater treatment,including degradation pathways,toxicity assessments and mechanistic insights,remain underexplored in the literature.This study presents novel S-scheme Mn_(0.5)Cd_(0.5)S/In_(2)S_(3)(MCS/IS)photocatalysts for efficient degradation of antibiotic pollutants,with a particular focus on tetracycline hydrochloride(TCH).The optimized MCS/IS photocatalyst demonstrates exceptional degradation efficiency and robust resistance to inorganic anions.Additionally,a continuous-flow wastewater treatment system,using an MCS/IS membrane,demonstrates outstanding stability in TCH photodegradation.Utilizing response surface methodology and Fukui function analysis,the effects of various parameters on photocatalytic degradation rates,along with the associated pathways and intermediate products,have been thoroughly investigated.Toxicity assessments confirm the environmental safety of the treated effluents.Mechanistic studies show that the S-scheme heterojunction in the MCS/IS photocatalyst improves electron-hole separation,thereby enhancing photocatalytic performance.It is expected that this study will serve as a model for advancing the removal of emerging contaminants,further enhancing photocatalytic AOPs as sustainable water purification technologies.展开更多
The rapid recombination of photogenerated carriers poses a significant limitation on the use of CdS quantum dots(QDs)in photocatalysis.Herein,the construction of a novel S-scheme heterojunction between cubic-phase CdS...The rapid recombination of photogenerated carriers poses a significant limitation on the use of CdS quantum dots(QDs)in photocatalysis.Herein,the construction of a novel S-scheme heterojunction between cubic-phase CdS QDs and hollow nanotube In_(2)O_(3)is successfully achieved using an electrostatic self-assembly method.Under visible light irradiation,all CdS-In_(2)O_(3)composites exhibit higher hydrogen evolution efficiency compared to pure CdS QDs.Notably,the photocatalytic H_(2)evolution rate of the optimal CdS-7%In_(2)O_(3)composite is determined to be 2258.59μmol g^(−1)h^(−1),approximately 12.3 times higher than that of pure CdS.The cyclic test indicates that the CdS-In_(2)O_(3)composite maintains considerable activity even after 5 cycles,indicating its excellent stability.In situ X-ray photoelectron spectroscopy and density functional theory calculations confirm that carrier migration in CdS-In_(2)O_(3)composites adheres to a typical S-scheme heterojunction mechanism.Additionally,a series of characterizations demonstrate that the formation of S-scheme heterojunctions between In_(2)O_(3)and CdS inhibits charge recombination and accelerates the separation and migration of photogenerated carriers in the CdS QDs,thus achieving enhanced photocatalytic performance.This work elucidates the pivotal role of S-scheme heterojunctions in photocatalytic H_(2)production and offers novel insights into the construction of effective composite photocatalysts.展开更多
Doping engineering is an effective strategy for graphitic carbon nitride(g-C_(3)N_(4))to improve its photocat-alytic hydrogen evolution reaction(HER)performance.In this work,a novel nitrogen and sulfur co-doped g-C_(3...Doping engineering is an effective strategy for graphitic carbon nitride(g-C_(3)N_(4))to improve its photocat-alytic hydrogen evolution reaction(HER)performance.In this work,a novel nitrogen and sulfur co-doped g-C_(3)N_(4)(N,S-g-C_(3)N_(4))is elaborately designed on the basis of theoretical predictions of first-principle density functional theory(DFT).The calculated Gibbs free energy of adsorbed hydrogen(ΔGH∗)for N,S-g-C_(3)N_(4) at the N-doping active sites is extremely close to zero(0.01 eV).Inspired by the theoretical predictions,the N,S-g-C_(3)N_(4) is successfully fabricated through ammonia-rich pyrolysis synthesis strategy,in which ammonia is in-situ obtained by pyrolyzing melamine.Subsequent characterizations indicate that the N,S-g-C_(3)N_(4) possesses high specific surface area,outstanding light utilization,good hydrophilicity,and efficient carrier transfer efficiency.Consequently,the N,S-g-C_(3)N_(4) displays an extremely high H2 evolution rate of 8269.9μmol g−1 h−1,achieves an apparent quantum efficiency(AQE)of 3.24%,and also possesses outsatnding durability.Theoretical calculations further demonstrate that N and S dopants can not only introduce doping energy level to reduce the band gap,but also induce charge redistribution to facilitate hydrogen adsorption,thus promoting the photocatalytic HER process.Moreover,femtosecond transient absorption(fs-TA)spectroscopy further corroborates the efficient photogenerated carrier transport of N,S-g-C_(3)N_(4).This research highlights a promising and reliable strategy to achieve superior photocatalytic activity,and exhibits significant guidance for precise designing high-efficiency photocatalysts.展开更多
Birefringent crystals play an irreplaceable role in optical systems by adjusting the polarization state of light in optical devices.This work successfully synthesized a new thiophosphate phase ofβ-Pb_(3)P_(2)S_(8)thr...Birefringent crystals play an irreplaceable role in optical systems by adjusting the polarization state of light in optical devices.This work successfully synthesized a new thiophosphate phase ofβ-Pb_(3)P_(2)S_(8)through the high-temperature solid-state spontaneous crystallization method.Different from the cubicα-Pb_(3)P_(2)S_(8),theβ-Pb_(3)P_(2)S_(8)crystallizes in the orthorhombic Pbcn space group.Notably,β-Pb_(3)P_(2)S_(8)shows a large band gap of 2.37 e V in lead-based chalcogenides,wide infrared transparent window(2.5-15μm),and excellent thermal stability.Importantly,the experimental birefringence shows the largest value of0.26@550 nm in chalcogenides,even larger than the commercialized oxide materials.The Barder charge analysis result indicates that the exceptional birefringence effect is mainly from the Pb^(2+)and S^(2-)in the[Pb S_n]polyhedrons.Meanwhile,the parallelly arranged polyhedral layers could improve the structural anisotropic.Therefore,this work supports a new method for designing chalcogenides with exceptional birefringence effect in the infrared region.展开更多
Traditional Pt/C electrode materials are prone to corrosion and detachment during H_(2)S detection,leading to a decrease in fuel cell-type sensor performance.Here,a high-performance H_(2)S sensor based on Pt loaded Ti...Traditional Pt/C electrode materials are prone to corrosion and detachment during H_(2)S detection,leading to a decrease in fuel cell-type sensor performance.Here,a high-performance H_(2)S sensor based on Pt loaded Ti_(3)C_(2)electrode material with-O/-OH terminal groups was designed and prepared.Experimental tests showed that the Pt/Ti_(3)C_(2)sensor has good sensitivity(0.162μA/ppm)and a very low detection limit to H_(2)S(10 ppb).After 90 days of stability testing,the response of the Pt/Ti_(3)C_(2)sensor shows a smaller decrease of 2%compared to that of the Pt/C sensor(22.9%).Meanwhile,the sensor also has high selectivity and repeatability.The density functional theory(DFT)calculation combined with the experiment results revealed that the improved H_(2)S sensing mechanism is attributed to the fact that the strong interaction between Pt and Ti_(3)C_(2)via the Pt-O-Ti bonding can reduce the formation energy of Pt and Ti_(3)C_(2),ultimately prolonging the sensor’s service life.Furthermore,the catalytic property of Pt can decrease the adsorption energy and dissociation barrier of H_(2)S on Pt/Ti_(3)C_(2)surface,greatly enhance the ability to generate protons and effectively transfer charges,realizing good sensitivity and high selectivity of the sensor.The sensor works at room temperature,making it very promising in the field of H_(2)S detection in future.展开更多
Piezoelectric effect,plasma effect and semiconductor heterostructure are important strategies for enhanced photocatalytic performance.Herein,we developed a novel heterostructure piezoelectric photocatalyst,Ag/Ag_(2)S/...Piezoelectric effect,plasma effect and semiconductor heterostructure are important strategies for enhanced photocatalytic performance.Herein,we developed a novel heterostructure piezoelectric photocatalyst,Ag/Ag_(2)S/BiFeO_(3)(AAS/BFO),for photocatalytic degradation of ciprofloxacin from water.Experimental results verified the enhancement of combining heterostructure piezoelectric polarization effect,which promotes efficient migration and separation of photogenerated carriers due to the localized surface plasmon resonance effect of Ag nanoparticles.Additionally,the introduction of Ag_(2)S constructs a new heterostructure,that enhances the electron transport rate and improves the separation efficiency on electron-hole pairs.Under ultrasonic stimulation and visible light irradiation,the degradation efficiencies of 15%-AAS/BFO towards ciprofloxacin,methyl orange and methylene blue are significantly enhanced compared to pure BFO fibers.The demonstrated AAS/BFO material based on the synergistic piezoelectric effect and plasmon heterostructure shows potential in efficient organic pollutants water treatment and transforming mechanical energy into chemical energy.展开更多
The reduction of carbon emissions in the steel industry is a significant challenge,and utilizing CO_(2) from carbon intensive steel industry off-gases for methanol production is a promising strategy for decarbonizatio...The reduction of carbon emissions in the steel industry is a significant challenge,and utilizing CO_(2) from carbon intensive steel industry off-gases for methanol production is a promising strategy for decarbonization.However,steelwork off-gases typically contain various impurities,including H_(2)S,which can deactivate commercial methanol synthesis catalysts,Cu/ZnO/Al_(2)O_(3)(CZA).Reverse water-gas shift(RWGS)reaction is the predominant side reaction in CO_(2) hydrogenation to methanol which can occur at ambient pressure,enabling the decouple of RWGS from methanol production at high pressure.Then,a series of activated CZA catalysts has been in-situ pretreated in 400 ppm H_(2)S/Ar at 250℃and tested for both RWGS reaction at ambient pressure and CO_(2) hydrogenation to methanol at high pressure.An innovative decoupling strategy was employed to isolate the RWGS reaction from the methanol synthesis process,enabling the investigation of the evolution of active site structures and the poisoning mechanism through elemental analysis,X-ray Diffraction,X-ray Photoelectron Spectroscopy,Fourier Transform Infrared Spectroscopy,Temperature Programmed Reduction and CO_(2) Temperature Programmed Desorption.The results indicate that there are different dynamic migration behaviors of ZnO_(x) in the two reaction systems,leading to different poisoning mechanisms.These interesting findings are beneficial to develop sulfur resistant and durable highly efficient catalysts for CO_(2) hydrogenation to methanol,promoting the carbon emission reduction in steel industry.展开更多
Developing efficient photocatalysts for CO_(2)conversion under full-spectrum irradiation remains a key challenge for solar-to-chemical energy conversion.In this study,a novel S-scheme heterojunction composed of reduct...Developing efficient photocatalysts for CO_(2)conversion under full-spectrum irradiation remains a key challenge for solar-to-chemical energy conversion.In this study,a novel S-scheme heterojunction composed of reduction Cs_(0.32)WO_(3)(CWO)nanosheets with hexagonal structure and oxidation WO_(3)·2H_(2)O(WO)nanorods with monoclinic structure photocatalyst was successfully constructed via an ultrasound strategy.Under full-spectrum irradiation for 4 h,the optimized 2D/1D of heterostructure CWO/WO-0.8 exhibited superior photocatalytic performance,achieving CO and CH_(3)OH yields of 29.74 and 63.71μmol·g^(-1),respectively.The enhanced activity is primarily ascribed to the formation of an S-scheme charge transfer pathway,which facilitates efficient separation and directional migration of photogenerated charge carriers through the internal electric field at the CWO/WO interface.This process facilitates the electron enrichment on the CWO surface and significantly enhances its CO_(2)reduction ability.Besides,the results of various characterizations show that CWO/WO-0.8 possesses enhanced optical response capability.The results of density functional theory calculations and CO_(2)-temperature programmed desorption analysis confirmed that the CWO/WO heterojunction exhibits stronger CO_(2)adsorption and activation abilities compared to the pristine CWO and WO.The reaction pathway for CH_(3)OH production was elucidated by in-situ diffused reflectance Fourier transformed infrared tests.This work provides new insights into the rational design of S-scheme photocatalysts for efficient and selective CO_(2)conversion.展开更多
The development of catalysts that can efficiently separate both bulk and interface charges is crucial for conversion and utilization of solar energy.In this study,a homo-heterojunction was fabricated by combin-ing twi...The development of catalysts that can efficiently separate both bulk and interface charges is crucial for conversion and utilization of solar energy.In this study,a homo-heterojunction was fabricated by combin-ing twinned-Cd_(0.5)Zn_(0.5)S(T-CZS)and Ni_(3)(PO_(4))_(2)with crystalline water(NiPO)using a solvent evaporation strategy for efficient photocatalytic H_(2)evolution in water containing degradable plastics.The bulk phase of T-CZS consists of wurtzite Cd_(0.5)Zn_(0.5)S(WZ-CZS)and zinc blende Cd_(0.5)Zn_(0.5)S(ZB-CZS),they exhibit a slight difference in energy range and can form S-scheme homojunction,while NiPO and T-CZS constitute the S-scheme heterojunction,they work together to promote the separation of bulk and interface charges.This double S-scheme homo-heterojunction achieves a hydrogen evolution rate(rH_(2))of 73.2 mmol h−1 g−1 over 8%NiPO/T-CZS in a solution mainly composed of polylactic acid(PLA),which exhibits an in-crease by factors of 243.0 and 4.5 compared to NiPO and T-CZS individually.Meanwhile,PLA plastics are degraded into organic chemicals including formic acid,acetic acid,and pyruvic acid.Moreover,NiPO ex-hibits(localized surface plasmon resonance)LSPR effect,which can broaden the light absorption range of the system,reduce the H_(2)evolution overpotential,and enhance electron utilization efficiency.Based on electron capture experiments and band theory analysis,the introducing of plastic as an electron donor further accelerates the evolution process of H_(2),while alkaline sodium hydroxide(NaOH)solution pro-motes the PLA dissociation and enhances oxidation driving force,indirectly promoting the H_(2)evolution kinetics of this system.The present research offers prospective solutions for engineering solar-powered H_(2)evolution to tackle energy challenges.展开更多
The construction of crystalline/amorphous g-C_(3)N_(4)homojunctions presents a versatile strategy to obtain all-organic homojunction photocatalysts with better interface matching and lower interface charge carrier mov...The construction of crystalline/amorphous g-C_(3)N_(4)homojunctions presents a versatile strategy to obtain all-organic homojunction photocatalysts with better interface matching and lower interface charge carrier movement resistance for optimized photocatalytic activity.However,the process entails a complex multi-step workup,which compromises its feasibility.To overcome this challenge,this work provided an innovative Na_(2)CO_(3)-induced crystallinity modulation strategy to construct a Na-doped crystalline/amorphous g-C_(3)N_(4)S-scheme homojunction photocatalyst in a single step.The approach involves the initial pre-assembling of melamine and cyanuric acid molecules,and subsequent introduction of Na_(2)CO_(3)before the calcination.Na_(2)CO_(3)plays key roles to induce in-situ crystallinity modulation during the calcination and as a source for Na-doping.The prepared g-C_(3)N_(4)S-scheme homojunction photocatalyst demonstrated a prominent H_(2)O_(2)-production rate of 444.6μmol·L^(-1)·h^(-1),which is 6.1-fold higher than that of bulk g-C_(3)N_(4).The enhanced activity was attributed to the synergistic effect of charge carrier separation induced by the S-scheme homojunction system,and the optimized interfacial H_(2)O_(2)generation kinetics.The latter was fostered by the Na-doping.This study provides an innovative approach for the one-step construction of g-C_(3)N_(4)S-scheme homojunction and its integration in photocatalytic applications.展开更多
文摘Emerging contaminants in water sources present serious environmental and health risks,creating an urgent need for efficient and reliable treatment strategies.Photocatalytic advanced oxidation processes(AOPs)provide rapid reaction rates and strong oxidation capabilities,however,comprehensive evaluations of wastewater treatment,including degradation pathways,toxicity assessments and mechanistic insights,remain underexplored in the literature.This study presents novel S-scheme Mn_(0.5)Cd_(0.5)S/In_(2)S_(3)(MCS/IS)photocatalysts for efficient degradation of antibiotic pollutants,with a particular focus on tetracycline hydrochloride(TCH).The optimized MCS/IS photocatalyst demonstrates exceptional degradation efficiency and robust resistance to inorganic anions.Additionally,a continuous-flow wastewater treatment system,using an MCS/IS membrane,demonstrates outstanding stability in TCH photodegradation.Utilizing response surface methodology and Fukui function analysis,the effects of various parameters on photocatalytic degradation rates,along with the associated pathways and intermediate products,have been thoroughly investigated.Toxicity assessments confirm the environmental safety of the treated effluents.Mechanistic studies show that the S-scheme heterojunction in the MCS/IS photocatalyst improves electron-hole separation,thereby enhancing photocatalytic performance.It is expected that this study will serve as a model for advancing the removal of emerging contaminants,further enhancing photocatalytic AOPs as sustainable water purification technologies.
文摘The rapid recombination of photogenerated carriers poses a significant limitation on the use of CdS quantum dots(QDs)in photocatalysis.Herein,the construction of a novel S-scheme heterojunction between cubic-phase CdS QDs and hollow nanotube In_(2)O_(3)is successfully achieved using an electrostatic self-assembly method.Under visible light irradiation,all CdS-In_(2)O_(3)composites exhibit higher hydrogen evolution efficiency compared to pure CdS QDs.Notably,the photocatalytic H_(2)evolution rate of the optimal CdS-7%In_(2)O_(3)composite is determined to be 2258.59μmol g^(−1)h^(−1),approximately 12.3 times higher than that of pure CdS.The cyclic test indicates that the CdS-In_(2)O_(3)composite maintains considerable activity even after 5 cycles,indicating its excellent stability.In situ X-ray photoelectron spectroscopy and density functional theory calculations confirm that carrier migration in CdS-In_(2)O_(3)composites adheres to a typical S-scheme heterojunction mechanism.Additionally,a series of characterizations demonstrate that the formation of S-scheme heterojunctions between In_(2)O_(3)and CdS inhibits charge recombination and accelerates the separation and migration of photogenerated carriers in the CdS QDs,thus achieving enhanced photocatalytic performance.This work elucidates the pivotal role of S-scheme heterojunctions in photocatalytic H_(2)production and offers novel insights into the construction of effective composite photocatalysts.
基金supported by the National Natural Science Foun-dation of China(No.62004143)the Key R&D Program of Hubei Province(No.2022BAA084)the Natural Science Foundation of Hubei Province(No.2021CFB133).
文摘Doping engineering is an effective strategy for graphitic carbon nitride(g-C_(3)N_(4))to improve its photocat-alytic hydrogen evolution reaction(HER)performance.In this work,a novel nitrogen and sulfur co-doped g-C_(3)N_(4)(N,S-g-C_(3)N_(4))is elaborately designed on the basis of theoretical predictions of first-principle density functional theory(DFT).The calculated Gibbs free energy of adsorbed hydrogen(ΔGH∗)for N,S-g-C_(3)N_(4) at the N-doping active sites is extremely close to zero(0.01 eV).Inspired by the theoretical predictions,the N,S-g-C_(3)N_(4) is successfully fabricated through ammonia-rich pyrolysis synthesis strategy,in which ammonia is in-situ obtained by pyrolyzing melamine.Subsequent characterizations indicate that the N,S-g-C_(3)N_(4) possesses high specific surface area,outstanding light utilization,good hydrophilicity,and efficient carrier transfer efficiency.Consequently,the N,S-g-C_(3)N_(4) displays an extremely high H2 evolution rate of 8269.9μmol g−1 h−1,achieves an apparent quantum efficiency(AQE)of 3.24%,and also possesses outsatnding durability.Theoretical calculations further demonstrate that N and S dopants can not only introduce doping energy level to reduce the band gap,but also induce charge redistribution to facilitate hydrogen adsorption,thus promoting the photocatalytic HER process.Moreover,femtosecond transient absorption(fs-TA)spectroscopy further corroborates the efficient photogenerated carrier transport of N,S-g-C_(3)N_(4).This research highlights a promising and reliable strategy to achieve superior photocatalytic activity,and exhibits significant guidance for precise designing high-efficiency photocatalysts.
基金supported in part by the National Natural Science Foundation of China(No.52102218)the National Key Research and Development Program of China(No.2020YFA0710303)+2 种基金the Fujian Science&Technology Innovation Laboratory for Op-toelectronic Information of China(No.2021ZZ127)the Minjiang Scholar Professorship(No.GXRC-21004)the Natural Science Foundation of Fujian Province of China(No.2021J01594)。
文摘Birefringent crystals play an irreplaceable role in optical systems by adjusting the polarization state of light in optical devices.This work successfully synthesized a new thiophosphate phase ofβ-Pb_(3)P_(2)S_(8)through the high-temperature solid-state spontaneous crystallization method.Different from the cubicα-Pb_(3)P_(2)S_(8),theβ-Pb_(3)P_(2)S_(8)crystallizes in the orthorhombic Pbcn space group.Notably,β-Pb_(3)P_(2)S_(8)shows a large band gap of 2.37 e V in lead-based chalcogenides,wide infrared transparent window(2.5-15μm),and excellent thermal stability.Importantly,the experimental birefringence shows the largest value of0.26@550 nm in chalcogenides,even larger than the commercialized oxide materials.The Barder charge analysis result indicates that the exceptional birefringence effect is mainly from the Pb^(2+)and S^(2-)in the[Pb S_n]polyhedrons.Meanwhile,the parallelly arranged polyhedral layers could improve the structural anisotropic.Therefore,this work supports a new method for designing chalcogenides with exceptional birefringence effect in the infrared region.
基金the National Key R&D Program of China(No.2023YFB3210102).
文摘Traditional Pt/C electrode materials are prone to corrosion and detachment during H_(2)S detection,leading to a decrease in fuel cell-type sensor performance.Here,a high-performance H_(2)S sensor based on Pt loaded Ti_(3)C_(2)electrode material with-O/-OH terminal groups was designed and prepared.Experimental tests showed that the Pt/Ti_(3)C_(2)sensor has good sensitivity(0.162μA/ppm)and a very low detection limit to H_(2)S(10 ppb).After 90 days of stability testing,the response of the Pt/Ti_(3)C_(2)sensor shows a smaller decrease of 2%compared to that of the Pt/C sensor(22.9%).Meanwhile,the sensor also has high selectivity and repeatability.The density functional theory(DFT)calculation combined with the experiment results revealed that the improved H_(2)S sensing mechanism is attributed to the fact that the strong interaction between Pt and Ti_(3)C_(2)via the Pt-O-Ti bonding can reduce the formation energy of Pt and Ti_(3)C_(2),ultimately prolonging the sensor’s service life.Furthermore,the catalytic property of Pt can decrease the adsorption energy and dissociation barrier of H_(2)S on Pt/Ti_(3)C_(2)surface,greatly enhance the ability to generate protons and effectively transfer charges,realizing good sensitivity and high selectivity of the sensor.The sensor works at room temperature,making it very promising in the field of H_(2)S detection in future.
基金supported by the National Natural Science Foundation of China(Nos.52372090 and 52073177)the National Natural Science Foundation of Guangdong,China(No.2023A1515010947)Shenzhen Basic Research Program(No.JCYJ20220531102207017).
文摘Piezoelectric effect,plasma effect and semiconductor heterostructure are important strategies for enhanced photocatalytic performance.Herein,we developed a novel heterostructure piezoelectric photocatalyst,Ag/Ag_(2)S/BiFeO_(3)(AAS/BFO),for photocatalytic degradation of ciprofloxacin from water.Experimental results verified the enhancement of combining heterostructure piezoelectric polarization effect,which promotes efficient migration and separation of photogenerated carriers due to the localized surface plasmon resonance effect of Ag nanoparticles.Additionally,the introduction of Ag_(2)S constructs a new heterostructure,that enhances the electron transport rate and improves the separation efficiency on electron-hole pairs.Under ultrasonic stimulation and visible light irradiation,the degradation efficiencies of 15%-AAS/BFO towards ciprofloxacin,methyl orange and methylene blue are significantly enhanced compared to pure BFO fibers.The demonstrated AAS/BFO material based on the synergistic piezoelectric effect and plasmon heterostructure shows potential in efficient organic pollutants water treatment and transforming mechanical energy into chemical energy.
基金supported by the National Natural Science Foundation of China(Nos.22276060 and 21976059)Guangdong Basic and Applied Basic Research Foundation(No.2024A1515012636)China Scholarship Council Scholarship(No.201906155006)。
文摘The reduction of carbon emissions in the steel industry is a significant challenge,and utilizing CO_(2) from carbon intensive steel industry off-gases for methanol production is a promising strategy for decarbonization.However,steelwork off-gases typically contain various impurities,including H_(2)S,which can deactivate commercial methanol synthesis catalysts,Cu/ZnO/Al_(2)O_(3)(CZA).Reverse water-gas shift(RWGS)reaction is the predominant side reaction in CO_(2) hydrogenation to methanol which can occur at ambient pressure,enabling the decouple of RWGS from methanol production at high pressure.Then,a series of activated CZA catalysts has been in-situ pretreated in 400 ppm H_(2)S/Ar at 250℃and tested for both RWGS reaction at ambient pressure and CO_(2) hydrogenation to methanol at high pressure.An innovative decoupling strategy was employed to isolate the RWGS reaction from the methanol synthesis process,enabling the investigation of the evolution of active site structures and the poisoning mechanism through elemental analysis,X-ray Diffraction,X-ray Photoelectron Spectroscopy,Fourier Transform Infrared Spectroscopy,Temperature Programmed Reduction and CO_(2) Temperature Programmed Desorption.The results indicate that there are different dynamic migration behaviors of ZnO_(x) in the two reaction systems,leading to different poisoning mechanisms.These interesting findings are beneficial to develop sulfur resistant and durable highly efficient catalysts for CO_(2) hydrogenation to methanol,promoting the carbon emission reduction in steel industry.
文摘Developing efficient photocatalysts for CO_(2)conversion under full-spectrum irradiation remains a key challenge for solar-to-chemical energy conversion.In this study,a novel S-scheme heterojunction composed of reduction Cs_(0.32)WO_(3)(CWO)nanosheets with hexagonal structure and oxidation WO_(3)·2H_(2)O(WO)nanorods with monoclinic structure photocatalyst was successfully constructed via an ultrasound strategy.Under full-spectrum irradiation for 4 h,the optimized 2D/1D of heterostructure CWO/WO-0.8 exhibited superior photocatalytic performance,achieving CO and CH_(3)OH yields of 29.74 and 63.71μmol·g^(-1),respectively.The enhanced activity is primarily ascribed to the formation of an S-scheme charge transfer pathway,which facilitates efficient separation and directional migration of photogenerated charge carriers through the internal electric field at the CWO/WO interface.This process facilitates the electron enrichment on the CWO surface and significantly enhances its CO_(2)reduction ability.Besides,the results of various characterizations show that CWO/WO-0.8 possesses enhanced optical response capability.The results of density functional theory calculations and CO_(2)-temperature programmed desorption analysis confirmed that the CWO/WO heterojunction exhibits stronger CO_(2)adsorption and activation abilities compared to the pristine CWO and WO.The reaction pathway for CH_(3)OH production was elucidated by in-situ diffused reflectance Fourier transformed infrared tests.This work provides new insights into the rational design of S-scheme photocatalysts for efficient and selective CO_(2)conversion.
基金financially supported by The Local Science and Development Fund Project Guided by the Central Govern-ment(No.24ZYQM001)the National Natural Science Foundation of China(Nos.22378326,11974276,and22078261)+6 种基金the Natural Science Basic Research Program of Shaanxi Province(No.2023-JC-YB-115)the Shaanxi Key Science and Technology Innovation Team Project(No.2022TD-33)the Qin Chuangyuan project of Shaanxi Province(No.QCYRCXM2022-213)the Basic Science Re-search Program of Shaanxi Basic Sciences Institute(Chemistry,Bi-ology,No.23JHQ081)the Key Research and Development Program of Shaanxi Province(No.2024GX-YBXM-449)the Initial Scientific Research Fund of Northwest University(S.Tao),Excellent Doctoral Dissertation Cultivation Program at Northwestern University(No.YB2024012)the Program of China Scholarship Council(No.202406970056)。
文摘The development of catalysts that can efficiently separate both bulk and interface charges is crucial for conversion and utilization of solar energy.In this study,a homo-heterojunction was fabricated by combin-ing twinned-Cd_(0.5)Zn_(0.5)S(T-CZS)and Ni_(3)(PO_(4))_(2)with crystalline water(NiPO)using a solvent evaporation strategy for efficient photocatalytic H_(2)evolution in water containing degradable plastics.The bulk phase of T-CZS consists of wurtzite Cd_(0.5)Zn_(0.5)S(WZ-CZS)and zinc blende Cd_(0.5)Zn_(0.5)S(ZB-CZS),they exhibit a slight difference in energy range and can form S-scheme homojunction,while NiPO and T-CZS constitute the S-scheme heterojunction,they work together to promote the separation of bulk and interface charges.This double S-scheme homo-heterojunction achieves a hydrogen evolution rate(rH_(2))of 73.2 mmol h−1 g−1 over 8%NiPO/T-CZS in a solution mainly composed of polylactic acid(PLA),which exhibits an in-crease by factors of 243.0 and 4.5 compared to NiPO and T-CZS individually.Meanwhile,PLA plastics are degraded into organic chemicals including formic acid,acetic acid,and pyruvic acid.Moreover,NiPO ex-hibits(localized surface plasmon resonance)LSPR effect,which can broaden the light absorption range of the system,reduce the H_(2)evolution overpotential,and enhance electron utilization efficiency.Based on electron capture experiments and band theory analysis,the introducing of plastic as an electron donor further accelerates the evolution process of H_(2),while alkaline sodium hydroxide(NaOH)solution pro-motes the PLA dissociation and enhances oxidation driving force,indirectly promoting the H_(2)evolution kinetics of this system.The present research offers prospective solutions for engineering solar-powered H_(2)evolution to tackle energy challenges.
文摘The construction of crystalline/amorphous g-C_(3)N_(4)homojunctions presents a versatile strategy to obtain all-organic homojunction photocatalysts with better interface matching and lower interface charge carrier movement resistance for optimized photocatalytic activity.However,the process entails a complex multi-step workup,which compromises its feasibility.To overcome this challenge,this work provided an innovative Na_(2)CO_(3)-induced crystallinity modulation strategy to construct a Na-doped crystalline/amorphous g-C_(3)N_(4)S-scheme homojunction photocatalyst in a single step.The approach involves the initial pre-assembling of melamine and cyanuric acid molecules,and subsequent introduction of Na_(2)CO_(3)before the calcination.Na_(2)CO_(3)plays key roles to induce in-situ crystallinity modulation during the calcination and as a source for Na-doping.The prepared g-C_(3)N_(4)S-scheme homojunction photocatalyst demonstrated a prominent H_(2)O_(2)-production rate of 444.6μmol·L^(-1)·h^(-1),which is 6.1-fold higher than that of bulk g-C_(3)N_(4).The enhanced activity was attributed to the synergistic effect of charge carrier separation induced by the S-scheme homojunction system,and the optimized interfacial H_(2)O_(2)generation kinetics.The latter was fostered by the Na-doping.This study provides an innovative approach for the one-step construction of g-C_(3)N_(4)S-scheme homojunction and its integration in photocatalytic applications.
