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
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。
