The development of an efficient artificial H_(2)O_(2) photosynthesis system is a challenging work using H_(2)O and O_(2) as starting materials.Herein,3D In_(2.77)S_(4) nanoflower precursor was in-situ deposited on K^(...The development of an efficient artificial H_(2)O_(2) photosynthesis system is a challenging work using H_(2)O and O_(2) as starting materials.Herein,3D In_(2.77)S_(4) nanoflower precursor was in-situ deposited on K^(+)-doped g-C_(3)N_(4)(KCN)nanosheets using a solvothermal method,then In_(2.77)S_(4)/KCN(IS/KCN)het-erojunction with an intimate interface was obtained after a calcination process.The investigation shows that the photocatalytic H_(2)O_(2) production rate of 50IS/KCN can reach up to 1.36 mmol g^(-1)h^(-1)without any sacrificial reagents under visible light irradiation,which is 9.2 times and 4.1 times higher than that of KCN and In_(2.77)S_(4)/respectively.The enhanced activity of the above composite can be mainly attributed to the S-scheme charge transfer route between KCN and In_(2.77)S_(4) according to density functional theory calculations,electron paramagnetic resonance and free radical capture tests,leading to an expanded light response range and rapid charge separation at their interface,as well as preserving the active electrons and holes for H_(2)O_(2) production.Besides,the unique 3D nanostructure and surface hydrophobicity of IS/KCN facilitate the diffusion and transportation of O_(2) around the active centers,the energy barriers of O_(2) protonation and H_(2)O_(2) desorption steps are ef-fectively reduced over the composite.In addition,this system also exhibits excellent light harvesting ability and stability.This work provides a potential strategy to explore a sustainable H_(2)O_(2) photo-synthesis pathway through the design of heterojunctions with intimate interfaces and desired reac-tion thermodynamics and kinetics.展开更多
Low cost,highly selective and efficient electrocatalysts for CO_(2)reduction reaction(CO_(2)RR)is crucial for lowering the global carbon footprint and mitigating energy shortages.Here,we first report a highly selectiv...Low cost,highly selective and efficient electrocatalysts for CO_(2)reduction reaction(CO_(2)RR)is crucial for lowering the global carbon footprint and mitigating energy shortages.Here,we first report a highly selective and efficient electrocatalyst for CO_(2)RR to CO using a surface-regulated Ni nanoparticles supported on N-doped CMK-3(N,O-Ni/CMK3).Compared with most Ni metal catalysts previously reported with severe competitive hydrogen evolution during the CO_(2)RR,the N,O-Ni/CMK3 catalyst presents a superior CO faradaic efficiency of about 97%,a high CO partial current density(13.01 mA cm^(-1))and turnover frequency(4.25 s^(–1)).The comprehensive characterization provides evidence that the N,O co-regulated Ni acts as the active center.Taking advantage of the N,O co-regulated chemical environment,N,O-Ni/CMK3 also displays a decent stability at negative potentials.Our work paves a novel approach for developing transition metal catalysts for CO_(2)RR with enhanced activity and selectivity via regulating surface chemical environment.展开更多
A novel nanocomposite of Ni nanoparticles loaded on Mg-doped Al_(2)O_(3)(Ni/Mg-Al_(2)O_(3))was prepared.By photothermocatalytic CO_(2) reduction with methane(CRM)merely using focused UV-vis-IR illumination on Ni/Mg-Al...A novel nanocomposite of Ni nanoparticles loaded on Mg-doped Al_(2)O_(3)(Ni/Mg-Al_(2)O_(3))was prepared.By photothermocatalytic CO_(2) reduction with methane(CRM)merely using focused UV-vis-IR illumination on Ni/Mg-Al_(2)O_(3),high production rates of H_(2)(r_(H2),69.71 mmol min^(−1) g^(−1))and CO(rCO,74.57 mmol min^(−1) g^(−1))and an extremely large light-to-fuel efficiency(η,32.9%)are acquired.High rH2 and rCO(51.07 and 59.66 mmol min^(−1) g^(−1))and a largeη(32.5%)are acquired even by using focusedλ>560 nm vis-IR illumination.Ni/Mg-Al_(2)O_(3) shows good durability for photothermocatalytic CRM due to the side reaction of carbon deposition being enormously inhibited in comparison with a reference catalyst of Ni nanoparticles loaded on Al_(2)O_(3).The enormous carbon deposition inhibition is ascribed to the presence of a fence of CO_(2) molecules(strongly adsorbed on Mg-doped Al_(2)O_(3))around Ni nanoparticles,which block the polymerization and growth of carbon species to nanofibers by promoting the oxidation of carbon species formed by CH_(4) dissociation.The high photothermocatalytic activity of Ni/Mg-Al_(2)O_(3) arises from efficient light-driven thermocatalytic CRM.A photoactivation is found to considerably raise the photothermocatalytic activity of Ni/Mg-Al_(2)O_(3) because of the apparent activation energy(Ea)being substantially decreased upon focused illumination.The Ea reduction is associated with the rate-determining steps of CRM(e.g.,CH_(4) dissociation and the oxidation of carbon species)being accelerated upon focused illumination.展开更多
Undoped and Ni–S co-doped mesoporous TiO2 nano materials were synthesized by using sol–gel method.The characteristic features of as prepared catalyst samples were investigated using various advanced spectroscopic an...Undoped and Ni–S co-doped mesoporous TiO2 nano materials were synthesized by using sol–gel method.The characteristic features of as prepared catalyst samples were investigated using various advanced spectroscopic and analytical techniques.The characterization results of the samples revealed that all the samples exhibited anatase phase(XRD),decreasing band gap(2.68 eV)(UV–Vis-DRS),small particle size(9.2 nm)(TEM),high surface area(142.156 m^2·g^-1)(BET),particles with spherical shape and smooth morphology(SEM);there is a frequency shift observed for co-doped sample(FT-IR)and the elemental composition electronic states and position of the doped elements(Ni and S)in the TiO2 lattice analyzed by XPS and EDX.These results supported the photocatalytic degradation of Bismarck Brown Red(BBR)achieved with in 110 min and also exhibited the antibacterial activity on Staphylococcus aureus(MTCC-3160),Pseudomonas fluorescence(MTCC-1688)under visible light irradiation.展开更多
TiO2 powder and TiO2 thin film on the surface of glazed ceramic tile were prepared by sol-gel method.The influences of different doping Cr3+ concentration on the photocatalytic activity of TiO2 were discussed, UV-visi...TiO2 powder and TiO2 thin film on the surface of glazed ceramic tile were prepared by sol-gel method.The influences of different doping Cr3+ concentration on the photocatalytic activity of TiO2 were discussed, UV-visible and X-ray diffraction analysis were used to test the performance of TiO2 powder and film. The results indicate that photocatalytic activity of doping Cr3+-TiO2 thin film is higher than that of powder, and the interaction between Cr3+-doped and substrate can greatly enhance the photocatalytic activity. The results of X-ray diffraction and photoabsorption show that the Cr3+ -doped energy level in TiO2 is 0. 62 eV high from the top of valence band, which belongs to the type of deep energy level doping. On the basis of the semiconductor energy level theory and Cr3+ dopant energy level, the semiconductor energy level model of Cr3+ in TiO2 powder and thin film were established, and the doping mechanisms of Cr3+-doped in TiO2 powder and thin film were analyzed.展开更多
Doping of foreign atoms and construction of unique structures are considered as effective approaches to design high-activity and strongdurability electrocatalysts.Herein,we report Fe-doped nickel hydroxide carbonate h...Doping of foreign atoms and construction of unique structures are considered as effective approaches to design high-activity and strongdurability electrocatalysts.Herein,we report Fe-doped nickel hydroxide carbonate hierarchical microtubes with Ag nanoparticles(denoted Ag/NiFeHC HMTs)through hydrolysis precipitation process.Experimental tests and density functional theory calculations reveal that Fe doping can tune the electron configuration to enhance the conductivity,markedly improve the electrochemical surface area to expose more active sites,and act as reactive centers to lower the free energy of the rate determination step.In addition,the unique hierarchical structure can also offer active sites and excellent cycling stability.Benefitting from these advantages,the as-obtained Ag/NiFeHC HMTs show excellent oxygen evolution reaction activity,with an overpotential of 208 mV at 10 mA cm^(−2)in 1.0M KOH.Also,it could achieve long-term stability at a current density of 20 mA cm^(−2)for 24 h.展开更多
Nanometer Cu singly doped and Cu/Al co-doped nickel hydroxides were synthesized by ultrasonic-assisted precipitation method. Their crystal structure, particle size, morphology, tap density and electrochemical performa...Nanometer Cu singly doped and Cu/Al co-doped nickel hydroxides were synthesized by ultrasonic-assisted precipitation method. Their crystal structure, particle size, morphology, tap density and electrochemical performance were investigated. The results show that the samples have a-phase structure with narrow particle size distribution. Cu singly doped nano-Ni（OH）2 contains irregular particles, while Cu/Al co-doped nano-Ni（OH）2 displays a quasi-spherical shape and has a relatively higher tap density. Composite electrodes were prepared by mixing 8% （mass fraction） nanometer samples with commercial micro-size spherical nickel. The charge/discharge test and cyclic voltammetry results indicate that the electrochemical performance of Cu/Al co-doped nano-Ni（OH）2 is better than that of Cu singly doped nano-Ni（OH）2, the former＇s discharge capacity reaches 330 mA.h/g at 0.2C, 12 mA.h/g and 91 mA.h/g larger than that of Cu singly doped sample and pure spherical nickel electrode, respectively. Moreover, the proton diffusion coefficient of Cu/Al co-doped sample is 52.3% larger than that of Cu singly doped sample.展开更多
基于试验数据,利用扩展有限元方法(extended finite element method,XFEM)和内聚力模型(cohesive zone model,CZM),对20Cr2Ni3钢顶头表面氧化膜的断裂行为进行了数值分析,研究了氧化膜受力方向和孔洞对裂纹生长行为的影响。结果表明:氧...基于试验数据,利用扩展有限元方法(extended finite element method,XFEM)和内聚力模型(cohesive zone model,CZM),对20Cr2Ni3钢顶头表面氧化膜的断裂行为进行了数值分析,研究了氧化膜受力方向和孔洞对裂纹生长行为的影响。结果表明:氧化膜受力方向影响裂纹扩展路径,外层氧化膜裂纹尖端的J积分和应力强度因子K_I随着θ角(受力方向与氧化膜的夹角)的增大而减小,当θ角增大到90°时裂纹停止生长;外层氧化膜上孔洞使得裂纹尖端的J积分和应力强度因子K_I减小。同时,孔洞的存在使得外力传递到内层氧化膜时产生应力集中和偏移,导致内层裂纹受力不均,减小了受力方向对内层裂纹生长的影响。展开更多
以硝酸镍为镍源、酸/碱性硅溶胶为硅源,采用共沉淀法制备了2种Ni/SiO_(2)催化剂。采用固定床反应器,评价Ni/SiO_(2)催化剂对于2-甲基呋喃(2-MF)气相加氢合成2-甲基四氢呋喃(2-MTHF)的反应性能。通过XRD、N_(2)等温吸附-脱附、H_(2)-TPR...以硝酸镍为镍源、酸/碱性硅溶胶为硅源,采用共沉淀法制备了2种Ni/SiO_(2)催化剂。采用固定床反应器,评价Ni/SiO_(2)催化剂对于2-甲基呋喃(2-MF)气相加氢合成2-甲基四氢呋喃(2-MTHF)的反应性能。通过XRD、N_(2)等温吸附-脱附、H_(2)-TPR、NH3-TPD、XPS、FTIR和TEM对催化剂进行了表征。考察了硅溶胶的酸碱性对Ni/SiO_(2)催化剂结构及性能的影响。结果表明,以酸性硅溶胶为硅源制备的Ni/SiO_(2)催化剂以弱酸中心酸量为主且存在中强酸中心,比表面积、平均孔径大,因而该催化剂加氢活性和2-MTHF的选择性较高。Ni/SiO_(2)催化剂稳定性良好,在最优反应条件〔温度90℃、H_(2)压力2 MPa、质量空速4.4 g 2-MF/(g催化剂·h)、H_(2)与2-MF物质的量之比为4∶1〕下进行催化剂稳定性测试(200 h),2-MF的转化率达到99.8%,2-MTHF的选择性均保持在97.5%左右。展开更多
文摘The development of an efficient artificial H_(2)O_(2) photosynthesis system is a challenging work using H_(2)O and O_(2) as starting materials.Herein,3D In_(2.77)S_(4) nanoflower precursor was in-situ deposited on K^(+)-doped g-C_(3)N_(4)(KCN)nanosheets using a solvothermal method,then In_(2.77)S_(4)/KCN(IS/KCN)het-erojunction with an intimate interface was obtained after a calcination process.The investigation shows that the photocatalytic H_(2)O_(2) production rate of 50IS/KCN can reach up to 1.36 mmol g^(-1)h^(-1)without any sacrificial reagents under visible light irradiation,which is 9.2 times and 4.1 times higher than that of KCN and In_(2.77)S_(4)/respectively.The enhanced activity of the above composite can be mainly attributed to the S-scheme charge transfer route between KCN and In_(2.77)S_(4) according to density functional theory calculations,electron paramagnetic resonance and free radical capture tests,leading to an expanded light response range and rapid charge separation at their interface,as well as preserving the active electrons and holes for H_(2)O_(2) production.Besides,the unique 3D nanostructure and surface hydrophobicity of IS/KCN facilitate the diffusion and transportation of O_(2) around the active centers,the energy barriers of O_(2) protonation and H_(2)O_(2) desorption steps are ef-fectively reduced over the composite.In addition,this system also exhibits excellent light harvesting ability and stability.This work provides a potential strategy to explore a sustainable H_(2)O_(2) photo-synthesis pathway through the design of heterojunctions with intimate interfaces and desired reac-tion thermodynamics and kinetics.
文摘Low cost,highly selective and efficient electrocatalysts for CO_(2)reduction reaction(CO_(2)RR)is crucial for lowering the global carbon footprint and mitigating energy shortages.Here,we first report a highly selective and efficient electrocatalyst for CO_(2)RR to CO using a surface-regulated Ni nanoparticles supported on N-doped CMK-3(N,O-Ni/CMK3).Compared with most Ni metal catalysts previously reported with severe competitive hydrogen evolution during the CO_(2)RR,the N,O-Ni/CMK3 catalyst presents a superior CO faradaic efficiency of about 97%,a high CO partial current density(13.01 mA cm^(-1))and turnover frequency(4.25 s^(–1)).The comprehensive characterization provides evidence that the N,O co-regulated Ni acts as the active center.Taking advantage of the N,O co-regulated chemical environment,N,O-Ni/CMK3 also displays a decent stability at negative potentials.Our work paves a novel approach for developing transition metal catalysts for CO_(2)RR with enhanced activity and selectivity via regulating surface chemical environment.
基金supported by National Natural Science Foundation of China(21972109,21673168)DFT calculations were conducted at the Shanghai Supercomputer Center(SSC),China.
文摘A novel nanocomposite of Ni nanoparticles loaded on Mg-doped Al_(2)O_(3)(Ni/Mg-Al_(2)O_(3))was prepared.By photothermocatalytic CO_(2) reduction with methane(CRM)merely using focused UV-vis-IR illumination on Ni/Mg-Al_(2)O_(3),high production rates of H_(2)(r_(H2),69.71 mmol min^(−1) g^(−1))and CO(rCO,74.57 mmol min^(−1) g^(−1))and an extremely large light-to-fuel efficiency(η,32.9%)are acquired.High rH2 and rCO(51.07 and 59.66 mmol min^(−1) g^(−1))and a largeη(32.5%)are acquired even by using focusedλ>560 nm vis-IR illumination.Ni/Mg-Al_(2)O_(3) shows good durability for photothermocatalytic CRM due to the side reaction of carbon deposition being enormously inhibited in comparison with a reference catalyst of Ni nanoparticles loaded on Al_(2)O_(3).The enormous carbon deposition inhibition is ascribed to the presence of a fence of CO_(2) molecules(strongly adsorbed on Mg-doped Al_(2)O_(3))around Ni nanoparticles,which block the polymerization and growth of carbon species to nanofibers by promoting the oxidation of carbon species formed by CH_(4) dissociation.The high photothermocatalytic activity of Ni/Mg-Al_(2)O_(3) arises from efficient light-driven thermocatalytic CRM.A photoactivation is found to considerably raise the photothermocatalytic activity of Ni/Mg-Al_(2)O_(3) because of the apparent activation energy(Ea)being substantially decreased upon focused illumination.The Ea reduction is associated with the rate-determining steps of CRM(e.g.,CH_(4) dissociation and the oxidation of carbon species)being accelerated upon focused illumination.
基金the University Grants Commission (UGC) for providing BSR fellowship
文摘Undoped and Ni–S co-doped mesoporous TiO2 nano materials were synthesized by using sol–gel method.The characteristic features of as prepared catalyst samples were investigated using various advanced spectroscopic and analytical techniques.The characterization results of the samples revealed that all the samples exhibited anatase phase(XRD),decreasing band gap(2.68 eV)(UV–Vis-DRS),small particle size(9.2 nm)(TEM),high surface area(142.156 m^2·g^-1)(BET),particles with spherical shape and smooth morphology(SEM);there is a frequency shift observed for co-doped sample(FT-IR)and the elemental composition electronic states and position of the doped elements(Ni and S)in the TiO2 lattice analyzed by XPS and EDX.These results supported the photocatalytic degradation of Bismarck Brown Red(BBR)achieved with in 110 min and also exhibited the antibacterial activity on Staphylococcus aureus(MTCC-3160),Pseudomonas fluorescence(MTCC-1688)under visible light irradiation.
基金Project (20466001) supported by the National Natural Science Foundation of China
文摘TiO2 powder and TiO2 thin film on the surface of glazed ceramic tile were prepared by sol-gel method.The influences of different doping Cr3+ concentration on the photocatalytic activity of TiO2 were discussed, UV-visible and X-ray diffraction analysis were used to test the performance of TiO2 powder and film. The results indicate that photocatalytic activity of doping Cr3+-TiO2 thin film is higher than that of powder, and the interaction between Cr3+-doped and substrate can greatly enhance the photocatalytic activity. The results of X-ray diffraction and photoabsorption show that the Cr3+ -doped energy level in TiO2 is 0. 62 eV high from the top of valence band, which belongs to the type of deep energy level doping. On the basis of the semiconductor energy level theory and Cr3+ dopant energy level, the semiconductor energy level model of Cr3+ in TiO2 powder and thin film were established, and the doping mechanisms of Cr3+-doped in TiO2 powder and thin film were analyzed.
基金Zhejiang Provincial Natural Science Foundation of China,Grant/Award Number:LQ20B010002。
文摘Doping of foreign atoms and construction of unique structures are considered as effective approaches to design high-activity and strongdurability electrocatalysts.Herein,we report Fe-doped nickel hydroxide carbonate hierarchical microtubes with Ag nanoparticles(denoted Ag/NiFeHC HMTs)through hydrolysis precipitation process.Experimental tests and density functional theory calculations reveal that Fe doping can tune the electron configuration to enhance the conductivity,markedly improve the electrochemical surface area to expose more active sites,and act as reactive centers to lower the free energy of the rate determination step.In addition,the unique hierarchical structure can also offer active sites and excellent cycling stability.Benefitting from these advantages,the as-obtained Ag/NiFeHC HMTs show excellent oxygen evolution reaction activity,with an overpotential of 208 mV at 10 mA cm^(−2)in 1.0M KOH.Also,it could achieve long-term stability at a current density of 20 mA cm^(−2)for 24 h.
基金Project (10774030) supported by the National Natural Science Foundation of ChinaProject (S2012010009955) supported by the Guangdong Province Natural Science Foundation of ChinaProject (12C232111916) supported by the Science and Technology Program of Guangzhou City of China
文摘Nanometer Cu singly doped and Cu/Al co-doped nickel hydroxides were synthesized by ultrasonic-assisted precipitation method. Their crystal structure, particle size, morphology, tap density and electrochemical performance were investigated. The results show that the samples have a-phase structure with narrow particle size distribution. Cu singly doped nano-Ni（OH）2 contains irregular particles, while Cu/Al co-doped nano-Ni（OH）2 displays a quasi-spherical shape and has a relatively higher tap density. Composite electrodes were prepared by mixing 8% （mass fraction） nanometer samples with commercial micro-size spherical nickel. The charge/discharge test and cyclic voltammetry results indicate that the electrochemical performance of Cu/Al co-doped nano-Ni（OH）2 is better than that of Cu singly doped nano-Ni（OH）2, the former＇s discharge capacity reaches 330 mA.h/g at 0.2C, 12 mA.h/g and 91 mA.h/g larger than that of Cu singly doped sample and pure spherical nickel electrode, respectively. Moreover, the proton diffusion coefficient of Cu/Al co-doped sample is 52.3% larger than that of Cu singly doped sample.
文摘基于试验数据,利用扩展有限元方法(extended finite element method,XFEM)和内聚力模型(cohesive zone model,CZM),对20Cr2Ni3钢顶头表面氧化膜的断裂行为进行了数值分析,研究了氧化膜受力方向和孔洞对裂纹生长行为的影响。结果表明:氧化膜受力方向影响裂纹扩展路径,外层氧化膜裂纹尖端的J积分和应力强度因子K_I随着θ角(受力方向与氧化膜的夹角)的增大而减小,当θ角增大到90°时裂纹停止生长;外层氧化膜上孔洞使得裂纹尖端的J积分和应力强度因子K_I减小。同时,孔洞的存在使得外力传递到内层氧化膜时产生应力集中和偏移,导致内层裂纹受力不均,减小了受力方向对内层裂纹生长的影响。
文摘以硝酸镍为镍源、酸/碱性硅溶胶为硅源,采用共沉淀法制备了2种Ni/SiO_(2)催化剂。采用固定床反应器,评价Ni/SiO_(2)催化剂对于2-甲基呋喃(2-MF)气相加氢合成2-甲基四氢呋喃(2-MTHF)的反应性能。通过XRD、N_(2)等温吸附-脱附、H_(2)-TPR、NH3-TPD、XPS、FTIR和TEM对催化剂进行了表征。考察了硅溶胶的酸碱性对Ni/SiO_(2)催化剂结构及性能的影响。结果表明,以酸性硅溶胶为硅源制备的Ni/SiO_(2)催化剂以弱酸中心酸量为主且存在中强酸中心,比表面积、平均孔径大,因而该催化剂加氢活性和2-MTHF的选择性较高。Ni/SiO_(2)催化剂稳定性良好,在最优反应条件〔温度90℃、H_(2)压力2 MPa、质量空速4.4 g 2-MF/(g催化剂·h)、H_(2)与2-MF物质的量之比为4∶1〕下进行催化剂稳定性测试(200 h),2-MF的转化率达到99.8%,2-MTHF的选择性均保持在97.5%左右。
