Pd catalyst with high activity and selectivity for O_(2)reduction to H_(2)O_(2)is highly desirable.However,metallic Pd catalyst suffers from limited activity and selectivity in H_(2)O_(2)photosynthesis due to intrinsi...Pd catalyst with high activity and selectivity for O_(2)reduction to H_(2)O_(2)is highly desirable.However,metallic Pd catalyst suffers from limited activity and selectivity in H_(2)O_(2)photosynthesis due to intrinsically strong O_(2)adsorption at Pd atom sites.Herein,a strategy is proposed to modulate the electronic structure,aiming to weaken O_(2)adsorption and further enhance O_(2)-reduction selectivity through the creation of highly dispersed and electron-enriched Pd^(δ-)atom sites.To achieve this,a novel photochemical plating approach is employed to selectively grow vertical Bi nanosheets on the(010)facet of BiVO_(4).This process confines highly dispersed Pd atoms within the Bi nanosheets,forming a PdBi cocatalyst that significantly boosts H_(2)O_(2)photosynthesis.Notably,the optimized PdBi/BiVO_(4)photocatalyst achieves a high H_(2)O_(2)production concentration of 2246.43μmol L−1,with an apparent quantum efficiency(AQE)of 11.16%,realizing a 1.74-fold enhancement in activity compared to Pd/BiVO_(4)(1289.28μmol L^(−1)).Theoretical calculation and experimental results confirm that the vertical-growth Bi nanosheets induce the formation of well-dispersed and electron-enriched Pd^(δ−)atom sites.This accordingly increases the antibonding-orbital occupancy of Pd-O_(ads),thereby weakening O_(2)adsorption and ultimately facilitating selective O_(2)reduction for photocatalytic H_(2)O_(2)production.This rational design of Pd-based catalysts provides a promising strategy for modulating the electronic structure of active atoms to advance artificial photosynthesis.展开更多
采用均匀沉淀法,以硫酸钛为前躯体,制备TiO_2-Bi_2O_3复合粉体材料。以罗丹明B为目标降解物,研究了热处理温度、催化剂用量对该复合材料光催化性能的影响。光催化活性随焙烧温度升高而增大,550℃焙烧的样品光催化活性高。当催化剂用量为...采用均匀沉淀法,以硫酸钛为前躯体,制备TiO_2-Bi_2O_3复合粉体材料。以罗丹明B为目标降解物,研究了热处理温度、催化剂用量对该复合材料光催化性能的影响。光催化活性随焙烧温度升高而增大,550℃焙烧的样品光催化活性高。当催化剂用量为0.026g/10 m L时,20 mg/L的罗丹明B溶液在紫外光照射100 min后,降解率可达到90%。该复合物对罗丹明B溶液的光催化降解符合一级动力学方程。展开更多
采用还原再氧化的烧结工艺制备了0.2 mol%Y_2O_3施主掺杂的95 mol%BaTiO_3-5 mol%(Bi_(1/2)Na_(1/2))TiO_3无铅正温度系数电阻(Positive temperature coefficient of resistivity,PTCR)陶瓷。研究发现,还原气氛下烧结的样品没有明显的P...采用还原再氧化的烧结工艺制备了0.2 mol%Y_2O_3施主掺杂的95 mol%BaTiO_3-5 mol%(Bi_(1/2)Na_(1/2))TiO_3无铅正温度系数电阻(Positive temperature coefficient of resistivity,PTCR)陶瓷。研究发现,还原气氛下烧结的样品没有明显的PTCR效应,需要进一步在空气中氧化处理。其中1200℃氧化2 h的样品PTCR性能最好,电阻突跳大于3个数量级。利用交流阻抗分析方法计算了材料的晶粒、晶界电阻,发现氧化后的陶瓷晶界电阻迅速增加,而晶粒电阻基本保持不变。最后根据Heywang-Jonker理论,计算了陶瓷晶界势垒高度、势垒宽度和受主浓度。展开更多
Exploring low-cost and highly active photocatalysts is very urgent to accomplish complete removal of phenolic contaminants and overcome the limitations of the existing photocatalysts.In this study,we designed and synt...Exploring low-cost and highly active photocatalysts is very urgent to accomplish complete removal of phenolic contaminants and overcome the limitations of the existing photocatalysts.In this study,we designed and synthesized noble metal-free TiO2 photocatalysts by introducing bismuth nanoparticles as modifiers of a TiO2 single crystal(Bi-SCTiO2).The Bi-SCTiO2 can make full use of the synergistic effect of a small band overlap and low charge carrier density(Bi)with a high conductivity(single crystal),significantly boosting the separation and migration of the photogenerated charge pairs.Therefore,the Bi-SCTiO2 photocatalyst exhibits a significantly enhanced degradation rate(12 times faster)of 4-nitrophenol than a TiO2 single crystal under simulated sunlight irradiation.Notably,the complete removal of phenolic contaminants is achieved in various water matrices,which not only successfully overcomes the incomplete degradation in many reported photocatalytic systems,but also manifests a significant practical potential for sewage disposal.Therefore,this work presents a new insight in designing and constructing noble metal-free decorated semiconductor single-crystal photocatalysts with excellent activity and cyclability.展开更多
A nanoheterojunction composite photocatalyst Bi2O3/TiO2 working under visible-light （λ≥ 420 nm） was prepared by combining two semiconductors Bi2O3 and TiO2 varying the Bi2O3/TiO2 molar ratio. Maleic acid was emplo...A nanoheterojunction composite photocatalyst Bi2O3/TiO2 working under visible-light （λ≥ 420 nm） was prepared by combining two semiconductors Bi2O3 and TiO2 varying the Bi2O3/TiO2 molar ratio. Maleic acid was employed as an organic binder to unite Bi2O3 and TiO2 nanoparticles. The SEM, TEM, XRD and diffuse reflectance spectra were utilized to characterize the prepared Bi2O3/TiO2 nanoheterojunction. The nanocomposite exhibited unusual high photocatalytic activity in decomposing 2-propanol in gas phase and phenol in aqueous phase and, evolution of CO2 under visible light irradiation while the end members exhibited low photocatalytic activity. The composite was optimized to 5 mol% Bi2O3/TiO2. The remarkable high photocatalytic efficiency originates from the unique relative energy band position of Bi2O3 and TiO2 as well as the absorption of visible light by Bi2O3.展开更多
An efficient synthesis of symmetrical 2,2-bis（1H-indol-3-yl）-2H-acenaphthen-1-one is achieved via a reaction of acenaphthe-nequinone and indoles catalyzed by solid superacid SO4^2-/TiO2 under solvent-free conditions...An efficient synthesis of symmetrical 2,2-bis（1H-indol-3-yl）-2H-acenaphthen-1-one is achieved via a reaction of acenaphthe-nequinone and indoles catalyzed by solid superacid SO4^2-/TiO2 under solvent-free conditions at room temperature by grinding, which provides an efficient route to the synthesis of symmetrical 2,2-bis（1H-indol-3-yl）-2H-acenaphthen-1-one.This procedure offers several advantages including solvent-free conditions,excellent yields of products,simple work-up as well as reuse of catalysts which makes it a useful and attractive protocol for the synthesis of these compounds.展开更多
基金supported by the National Natural Science Foundation of China(22178276,221760110,22178275)the Postdoctoral Fellowship Program of CPSF(GZC20240888)the Postdoctoral Project of Hubei Province(2024HBBHCXB053).
文摘Pd catalyst with high activity and selectivity for O_(2)reduction to H_(2)O_(2)is highly desirable.However,metallic Pd catalyst suffers from limited activity and selectivity in H_(2)O_(2)photosynthesis due to intrinsically strong O_(2)adsorption at Pd atom sites.Herein,a strategy is proposed to modulate the electronic structure,aiming to weaken O_(2)adsorption and further enhance O_(2)-reduction selectivity through the creation of highly dispersed and electron-enriched Pd^(δ-)atom sites.To achieve this,a novel photochemical plating approach is employed to selectively grow vertical Bi nanosheets on the(010)facet of BiVO_(4).This process confines highly dispersed Pd atoms within the Bi nanosheets,forming a PdBi cocatalyst that significantly boosts H_(2)O_(2)photosynthesis.Notably,the optimized PdBi/BiVO_(4)photocatalyst achieves a high H_(2)O_(2)production concentration of 2246.43μmol L−1,with an apparent quantum efficiency(AQE)of 11.16%,realizing a 1.74-fold enhancement in activity compared to Pd/BiVO_(4)(1289.28μmol L^(−1)).Theoretical calculation and experimental results confirm that the vertical-growth Bi nanosheets induce the formation of well-dispersed and electron-enriched Pd^(δ−)atom sites.This accordingly increases the antibonding-orbital occupancy of Pd-O_(ads),thereby weakening O_(2)adsorption and ultimately facilitating selective O_(2)reduction for photocatalytic H_(2)O_(2)production.This rational design of Pd-based catalysts provides a promising strategy for modulating the electronic structure of active atoms to advance artificial photosynthesis.
文摘采用均匀沉淀法,以硫酸钛为前躯体,制备TiO_2-Bi_2O_3复合粉体材料。以罗丹明B为目标降解物,研究了热处理温度、催化剂用量对该复合材料光催化性能的影响。光催化活性随焙烧温度升高而增大,550℃焙烧的样品光催化活性高。当催化剂用量为0.026g/10 m L时,20 mg/L的罗丹明B溶液在紫外光照射100 min后,降解率可达到90%。该复合物对罗丹明B溶液的光催化降解符合一级动力学方程。
文摘采用还原再氧化的烧结工艺制备了0.2 mol%Y_2O_3施主掺杂的95 mol%BaTiO_3-5 mol%(Bi_(1/2)Na_(1/2))TiO_3无铅正温度系数电阻(Positive temperature coefficient of resistivity,PTCR)陶瓷。研究发现,还原气氛下烧结的样品没有明显的PTCR效应,需要进一步在空气中氧化处理。其中1200℃氧化2 h的样品PTCR性能最好,电阻突跳大于3个数量级。利用交流阻抗分析方法计算了材料的晶粒、晶界电阻,发现氧化后的陶瓷晶界电阻迅速增加,而晶粒电阻基本保持不变。最后根据Heywang-Jonker理论,计算了陶瓷晶界势垒高度、势垒宽度和受主浓度。
文摘Exploring low-cost and highly active photocatalysts is very urgent to accomplish complete removal of phenolic contaminants and overcome the limitations of the existing photocatalysts.In this study,we designed and synthesized noble metal-free TiO2 photocatalysts by introducing bismuth nanoparticles as modifiers of a TiO2 single crystal(Bi-SCTiO2).The Bi-SCTiO2 can make full use of the synergistic effect of a small band overlap and low charge carrier density(Bi)with a high conductivity(single crystal),significantly boosting the separation and migration of the photogenerated charge pairs.Therefore,the Bi-SCTiO2 photocatalyst exhibits a significantly enhanced degradation rate(12 times faster)of 4-nitrophenol than a TiO2 single crystal under simulated sunlight irradiation.Notably,the complete removal of phenolic contaminants is achieved in various water matrices,which not only successfully overcomes the incomplete degradation in many reported photocatalytic systems,but also manifests a significant practical potential for sewage disposal.Therefore,this work presents a new insight in designing and constructing noble metal-free decorated semiconductor single-crystal photocatalysts with excellent activity and cyclability.
文摘A nanoheterojunction composite photocatalyst Bi2O3/TiO2 working under visible-light （λ≥ 420 nm） was prepared by combining two semiconductors Bi2O3 and TiO2 varying the Bi2O3/TiO2 molar ratio. Maleic acid was employed as an organic binder to unite Bi2O3 and TiO2 nanoparticles. The SEM, TEM, XRD and diffuse reflectance spectra were utilized to characterize the prepared Bi2O3/TiO2 nanoheterojunction. The nanocomposite exhibited unusual high photocatalytic activity in decomposing 2-propanol in gas phase and phenol in aqueous phase and, evolution of CO2 under visible light irradiation while the end members exhibited low photocatalytic activity. The composite was optimized to 5 mol% Bi2O3/TiO2. The remarkable high photocatalytic efficiency originates from the unique relative energy band position of Bi2O3 and TiO2 as well as the absorption of visible light by Bi2O3.
基金supported by the research foundation of Hebei University of Science and Technology
文摘An efficient synthesis of symmetrical 2,2-bis（1H-indol-3-yl）-2H-acenaphthen-1-one is achieved via a reaction of acenaphthe-nequinone and indoles catalyzed by solid superacid SO4^2-/TiO2 under solvent-free conditions at room temperature by grinding, which provides an efficient route to the synthesis of symmetrical 2,2-bis（1H-indol-3-yl）-2H-acenaphthen-1-one.This procedure offers several advantages including solvent-free conditions,excellent yields of products,simple work-up as well as reuse of catalysts which makes it a useful and attractive protocol for the synthesis of these compounds.
