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
Photocatalytic hydrogen evolution from water splitting is an appealing method for producing clean chemical fuels.Cu_(2)O,with a suitable bandgap,holds promise as a semiconductor for this process.However,the strong pho...Photocatalytic hydrogen evolution from water splitting is an appealing method for producing clean chemical fuels.Cu_(2)O,with a suitable bandgap,holds promise as a semiconductor for this process.However,the strong photo-corrosion and rapid charge recombination of Cu_(2)O strongly limit its application in the photocatalytic fields.Herein,an S-scheme heterojunction photocatalyst composed of TiO_(2)and Cu_(2)O was rationally designed to effectively avoid the photo-corrosion of Cu_(2)O.The introduction of an interfacial nitrogen-doped carbon(NC)layer switches the heterojunction interfacial charge transfer pathway from the p-n to S-scheme heterojunction,which avoids excessive accumulation of photogenerated holes on the surface of Cu_(2)O.Meanwhile,the hybrid structure shows a broad spectral response(300-800 nm)and efficient charge separation and transfer efficiency.Interestingly,the highest photocatalytic hydrogen evolution rate of TiO_(2)-NC-3%Cu_(2)O-3%Ni is 13521.9μmol g^(-1)h^(-1),which is approximately 664.1 times higher than that of pure Cu_(2)O.In-situ X-ray photoelectron spectroscopy and Kelvin probe confirm the charge transfer mechanism of S-scheme heterojunction.The formation of S-scheme heterojunctions effectively accelerates the separation of photogenerated electron-hole pairs and enhances redox capacity,thereby improving the photocatalytic performance and stability of Cu_(2)O.This study provides valuable insights into the rational design of highly efficient Cu_(2)O-based heterojunction photocatalysts for hydrogen production.展开更多
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.
基金X.Li thanks the National Natural Science Foundation of China(Nos.21975084 and 51672089)the Natural Science Foundation of Guangdong Province(No.2021A1515010075)for their support.X.Peng thanks the State Key Laboratory of Pollution Control and Resource Reuse Foundation(No.PCRRF21028)for the support.
文摘Photocatalytic hydrogen evolution from water splitting is an appealing method for producing clean chemical fuels.Cu_(2)O,with a suitable bandgap,holds promise as a semiconductor for this process.However,the strong photo-corrosion and rapid charge recombination of Cu_(2)O strongly limit its application in the photocatalytic fields.Herein,an S-scheme heterojunction photocatalyst composed of TiO_(2)and Cu_(2)O was rationally designed to effectively avoid the photo-corrosion of Cu_(2)O.The introduction of an interfacial nitrogen-doped carbon(NC)layer switches the heterojunction interfacial charge transfer pathway from the p-n to S-scheme heterojunction,which avoids excessive accumulation of photogenerated holes on the surface of Cu_(2)O.Meanwhile,the hybrid structure shows a broad spectral response(300-800 nm)and efficient charge separation and transfer efficiency.Interestingly,the highest photocatalytic hydrogen evolution rate of TiO_(2)-NC-3%Cu_(2)O-3%Ni is 13521.9μmol g^(-1)h^(-1),which is approximately 664.1 times higher than that of pure Cu_(2)O.In-situ X-ray photoelectron spectroscopy and Kelvin probe confirm the charge transfer mechanism of S-scheme heterojunction.The formation of S-scheme heterojunctions effectively accelerates the separation of photogenerated electron-hole pairs and enhances redox capacity,thereby improving the photocatalytic performance and stability of Cu_(2)O.This study provides valuable insights into the rational design of highly efficient Cu_(2)O-based heterojunction photocatalysts for hydrogen production.
基金the National Natural Science Foundation of China(22378148,21975084,51672089)the Natural Science Foundation of Guangdong Province(2021A1515010075)for their supports。
