Photocatalytic splitting of water over p-type semiconductors is a promising strategy for production of hydrogen.However,the determination of rate law is rarely reported.To this purpose,copper oxide(CuO)is selected as ...Photocatalytic splitting of water over p-type semiconductors is a promising strategy for production of hydrogen.However,the determination of rate law is rarely reported.To this purpose,copper oxide(CuO)is selected as a model photocathode in this study,and the photogenerated surface charge density,interfacial charge transfer rate constant and their relation to the water reduction rate(in terms of photocurrent)were investigated by a combination of(photo)electrochemical techniques.The results showed that the charge transfer rate constant is exponential-dependent on the surface charge density,and that the photocurrent equals to the product of the charge transfer rate constant and surface charge density.The reaction is first-order in terms of surface charge density.Such an unconventional rate law contrasts with the reports in literature.The charge density-dependent rate constant results from the Fermi level pinning(i.e.,Galvani potential is the main driving force for the reaction)due to accumulation of charge in the surface states and/or Frumkin behavior(i.e.,chemical potential is the main driving force).This study,therefore,may be helpful for further investigation on the mechanism of hydrogen evolution over a CuO photocathode and for designing more efficient CuO-based photocatalysts.展开更多
岩石-混凝土界面是工程结构的薄弱环节,对结构整体的强度和稳定性有重要影响。为反映岩-混界面天然粗糙状态,基于内聚力模型(cohesive zone model,简称CZM),建立了具有随机生成粗糙界面的岩石-混凝土复合巴西圆盘试件数值模型,通过不同...岩石-混凝土界面是工程结构的薄弱环节,对结构整体的强度和稳定性有重要影响。为反映岩-混界面天然粗糙状态,基于内聚力模型(cohesive zone model,简称CZM),建立了具有随机生成粗糙界面的岩石-混凝土复合巴西圆盘试件数值模型,通过不同加载角度下的巴西劈裂物理试验验证了该方法的可靠性,并探究了界面粗糙度、加载角度对试件峰值荷载和破坏特征的影响。结果表明:不同加载角度下,试件存在3种典型破坏模式:界面黏结破坏、复合破坏、双材料拉伸开裂破坏;加载角度对试件力学行为的影响以70°为界,加载角度小于70°时影响显著,大于70°后影响不显著;界面粗糙度的影响随加载角度的不同有较大差异,当加载角度在15°~65°范围内,提高界面粗糙度可显著提高试件峰值荷载,增强岩-混结构的承载能力;界面处应力状态的差异决定了试件破坏模式的不同,但粗糙的界面可以增强混凝土与岩石之间的黏结和互锁效应,对试件破坏模式产生影响。研究结果将加深对岩石-混凝土界面破坏机制的认识,对工程建设具有指导意义。展开更多
为了研究高温和应变率对超高性能混凝土(UHPC)劈裂抗拉性能的影响,对不同温度(20、105、200、300、400℃)作用后UHPC的质量损失率、抗压强度、弹性模量、静态和动态(应变率为1.8~6.8 s^(-1))劈裂抗拉强度进行了测试.结果表明:以2~10℃/...为了研究高温和应变率对超高性能混凝土(UHPC)劈裂抗拉性能的影响,对不同温度(20、105、200、300、400℃)作用后UHPC的质量损失率、抗压强度、弹性模量、静态和动态(应变率为1.8~6.8 s^(-1))劈裂抗拉强度进行了测试.结果表明:以2~10℃/min的加热速率升温至400℃后,所有试件均在保温期间发生爆裂性剥落;U H P C的抗压强度、弹性模量、静态劈裂抗拉强度均随温度增大而提高,300℃作用后比常温时分别提高了13.2%、19.1%和17.3%;动态劈裂抗拉强度和耗散能均具有明显的应变率效应,当应变率从1.8~2.2 s^(-1)增加到6.3~6.8 s^(-1)时,20~300℃作用后的UHPC动态劈裂抗拉强度和耗散能分别提高了69.1%~74.1%和146.7%~177.6%;高温作用后UHPC中C-S-H表面的吸附水、孔隙内自由水和凝胶结合水先后分解,增大了试件的质量损失率;基体内高温和高压环境促进了水泥水化反应和硅灰火山灰反应,提升了UHPC的致密程度,增强了钢纤维的桥连作用;在冲击荷载作用下,基体开裂速度的加快和由钢纤维拔出所致基体摩擦效应的增强导致耗散能增大.展开更多
基金the National Basic Research Development of China(2011CB936003)the National Natural Science Foundation of China(50971116)。
文摘Photocatalytic splitting of water over p-type semiconductors is a promising strategy for production of hydrogen.However,the determination of rate law is rarely reported.To this purpose,copper oxide(CuO)is selected as a model photocathode in this study,and the photogenerated surface charge density,interfacial charge transfer rate constant and their relation to the water reduction rate(in terms of photocurrent)were investigated by a combination of(photo)electrochemical techniques.The results showed that the charge transfer rate constant is exponential-dependent on the surface charge density,and that the photocurrent equals to the product of the charge transfer rate constant and surface charge density.The reaction is first-order in terms of surface charge density.Such an unconventional rate law contrasts with the reports in literature.The charge density-dependent rate constant results from the Fermi level pinning(i.e.,Galvani potential is the main driving force for the reaction)due to accumulation of charge in the surface states and/or Frumkin behavior(i.e.,chemical potential is the main driving force).This study,therefore,may be helpful for further investigation on the mechanism of hydrogen evolution over a CuO photocathode and for designing more efficient CuO-based photocatalysts.
文摘岩石-混凝土界面是工程结构的薄弱环节,对结构整体的强度和稳定性有重要影响。为反映岩-混界面天然粗糙状态,基于内聚力模型(cohesive zone model,简称CZM),建立了具有随机生成粗糙界面的岩石-混凝土复合巴西圆盘试件数值模型,通过不同加载角度下的巴西劈裂物理试验验证了该方法的可靠性,并探究了界面粗糙度、加载角度对试件峰值荷载和破坏特征的影响。结果表明:不同加载角度下,试件存在3种典型破坏模式:界面黏结破坏、复合破坏、双材料拉伸开裂破坏;加载角度对试件力学行为的影响以70°为界,加载角度小于70°时影响显著,大于70°后影响不显著;界面粗糙度的影响随加载角度的不同有较大差异,当加载角度在15°~65°范围内,提高界面粗糙度可显著提高试件峰值荷载,增强岩-混结构的承载能力;界面处应力状态的差异决定了试件破坏模式的不同,但粗糙的界面可以增强混凝土与岩石之间的黏结和互锁效应,对试件破坏模式产生影响。研究结果将加深对岩石-混凝土界面破坏机制的认识,对工程建设具有指导意义。
文摘为了研究高温和应变率对超高性能混凝土(UHPC)劈裂抗拉性能的影响,对不同温度(20、105、200、300、400℃)作用后UHPC的质量损失率、抗压强度、弹性模量、静态和动态(应变率为1.8~6.8 s^(-1))劈裂抗拉强度进行了测试.结果表明:以2~10℃/min的加热速率升温至400℃后,所有试件均在保温期间发生爆裂性剥落;U H P C的抗压强度、弹性模量、静态劈裂抗拉强度均随温度增大而提高,300℃作用后比常温时分别提高了13.2%、19.1%和17.3%;动态劈裂抗拉强度和耗散能均具有明显的应变率效应,当应变率从1.8~2.2 s^(-1)增加到6.3~6.8 s^(-1)时,20~300℃作用后的UHPC动态劈裂抗拉强度和耗散能分别提高了69.1%~74.1%和146.7%~177.6%;高温作用后UHPC中C-S-H表面的吸附水、孔隙内自由水和凝胶结合水先后分解,增大了试件的质量损失率;基体内高温和高压环境促进了水泥水化反应和硅灰火山灰反应,提升了UHPC的致密程度,增强了钢纤维的桥连作用;在冲击荷载作用下,基体开裂速度的加快和由钢纤维拔出所致基体摩擦效应的增强导致耗散能增大.
