Yolk-shell architectures have attracted extensive attention owing to their unique structure and infusive applications. MoS2 is regarded as one of the most promising catalytic materials for hydrogen evolution by the sp...Yolk-shell architectures have attracted extensive attention owing to their unique structure and infusive applications. MoS2 is regarded as one of the most promising catalytic materials for hydrogen evolution by the splitting of water. In this work, a simple self-template solvothermal approach is developed for the synthesis of novel MoS2 yolk-shell microspheres with a hierarchical porous structure by reacting MoO2 microspheres with L-cysteine. A dissolution- recrystallization formation mechanism is proposed for the MoS2 yolk-shell microspheres. Owing to structural superiority, the new material architecture exhibits improved photoelectrochemical properties, including efficient hydrogen evolution reaction catalytic activities, a high photocurrent density, a small overpotential, and a low charge-transfer resistance.展开更多
钼硫化物被认为是一种高效的电催化析氢反应的催化剂,因此其合成方法受到了广泛的研究和关注。本文以四硫代钼酸铵和氧化石墨为前驱体,利用γ射线对其辐照还原,一步法制备了钼硫化物/还原氧化石墨烯(Mo S_x/RGO)复合材料。通过X射线光...钼硫化物被认为是一种高效的电催化析氢反应的催化剂,因此其合成方法受到了广泛的研究和关注。本文以四硫代钼酸铵和氧化石墨为前驱体,利用γ射线对其辐照还原,一步法制备了钼硫化物/还原氧化石墨烯(Mo S_x/RGO)复合材料。通过X射线光电子能谱、X射线衍射、透射电子显微镜、Raman光谱等表征手段确认复合材料中的Mo Sx为无定型结构,且氧化石墨烯得到了有效的还原。同时系统研究了吸收剂量、前驱体配比对复合材料作为析氢反应催化剂性能的影响。结果发现,Mo Sx/RGO复合材料具有优异的催化性能,其催化起始电压为110 m V,在电流密度为10 m A·cm^(-2)时过电势仅为160 m V,Tafel斜率为46 m V·dec^(-1),说明该催化剂催化析氢机理为Volmer-Heyrovesy机理。此外,Mo Sx/RGO复合材料还具有良好的催化稳定性。展开更多
电解水技术是一种生产高纯氢燃料的方法,能够增强可再生能源发电系统的消纳能力.相较于质子交换膜(PEM)电解槽,碱性(ALK)电解槽可以使用非贵金属基催化电极,拥有更高的经济效益和市场占有率.然而,由于ALK电解槽处于质子稀缺环境,阴极氢...电解水技术是一种生产高纯氢燃料的方法,能够增强可再生能源发电系统的消纳能力.相较于质子交换膜(PEM)电解槽,碱性(ALK)电解槽可以使用非贵金属基催化电极,拥有更高的经济效益和市场占有率.然而,由于ALK电解槽处于质子稀缺环境,阴极氢气演化反应(HER)动力学变得更加复杂,需要快速解离水分子提供动态质子微环境.硫化钼(MoS_(2))纳米片边缘具有合适的质子吸附和演化的活性位点,是制备HER催化剂的潜力材料.但其二维基面原子由于配位饱和,显示出较弱的质子吸附能力.如何调控MoS_(2)基面以实现水解动力与质子吸附演化动力的集成,提升MoS_(2)纳米片的碱性HER活性,具有重要的科学和应用意义.本文提出了一种Co/O双原子植入策略,精准调控双活性位点及其电子结构,实现了水解离动力和质子吸附演化动力的高效耦联.首先,利用刻蚀和电沉积的两步实验法,在MoS_(2)基面上成功引入O和Co原子;随后,结合高分辨透射电镜、高角环形暗场-扫描透射电子显微镜、同步辐射X射线吸收精细结构谱等表征分析技术,精准识别了掺杂Co/O原子的位置和配位情况:O原子替换部分S原子,Co原子占据Mo原子的上方,构建出立体凸起的“O-Co-S_(2)”配位构型.催化在线的原位表征分析结果表明:该独特的“O-Co-S_(2)”原子基序发挥着水解离与氢演化反应协同催化效应.密度泛函理论计算结果也证实了该协同机制,其中Co位点促进水的解离反应,而S位点则有助于质子的转化生成氢气.因此,Co/O掺杂MoS_(2)催化剂(Co-O@MoS_(2))表现出较好的碱性HER活性:仅需81 mV的过电位,即可达到100 mA cm^(‒2)的电流密度,Tafel斜率低至42 mV dec^(‒1),在600 mA cm^(‒2)的高电流密度测试中运行300 h活性无衰减.上述碱性HER性能不仅远高于原始的MoS_(2)纳米片,而且也领先于部分已报道结果.综上所述,本文在MoS_(2)基面上构筑了原�展开更多
A series of unsupported MoS2 catalysts with or without Al2O3 modification was prepared using a modified thermal decomposition approach. The catalysts were tested for the methanation of carbon monoxide and the optimum ...A series of unsupported MoS2 catalysts with or without Al2O3 modification was prepared using a modified thermal decomposition approach. The catalysts were tested for the methanation of carbon monoxide and the optimum one has 25.6wt-% Al2O3 content. The catalysts were characterized by nitrogen adsorption measurement, X-ray diffraction and transmission electron microscopy. The results show that adding appropriate amount of Al2O3 increases the dispersion of MoS2, and the increased interaction force between MoS2 and Al2O3 can inhibit the sintering of active MoS2 to some extent.展开更多
基金This work received financial support from the Dean Fund of Chinese Academy of Inspection and Quaran- tine （No. 2016JK025）, the Science Foundation of Administration of Quality Supervision, Inspection and Quarantine （AQSIQ） （No. 2015IK308）, and the National Natural Science Foundation of China （No. 51472226）.
文摘Yolk-shell architectures have attracted extensive attention owing to their unique structure and infusive applications. MoS2 is regarded as one of the most promising catalytic materials for hydrogen evolution by the splitting of water. In this work, a simple self-template solvothermal approach is developed for the synthesis of novel MoS2 yolk-shell microspheres with a hierarchical porous structure by reacting MoO2 microspheres with L-cysteine. A dissolution- recrystallization formation mechanism is proposed for the MoS2 yolk-shell microspheres. Owing to structural superiority, the new material architecture exhibits improved photoelectrochemical properties, including efficient hydrogen evolution reaction catalytic activities, a high photocurrent density, a small overpotential, and a low charge-transfer resistance.
文摘钼硫化物被认为是一种高效的电催化析氢反应的催化剂,因此其合成方法受到了广泛的研究和关注。本文以四硫代钼酸铵和氧化石墨为前驱体,利用γ射线对其辐照还原,一步法制备了钼硫化物/还原氧化石墨烯(Mo S_x/RGO)复合材料。通过X射线光电子能谱、X射线衍射、透射电子显微镜、Raman光谱等表征手段确认复合材料中的Mo Sx为无定型结构,且氧化石墨烯得到了有效的还原。同时系统研究了吸收剂量、前驱体配比对复合材料作为析氢反应催化剂性能的影响。结果发现,Mo Sx/RGO复合材料具有优异的催化性能,其催化起始电压为110 m V,在电流密度为10 m A·cm^(-2)时过电势仅为160 m V,Tafel斜率为46 m V·dec^(-1),说明该催化剂催化析氢机理为Volmer-Heyrovesy机理。此外,Mo Sx/RGO复合材料还具有良好的催化稳定性。
文摘在316L不锈钢网基底上利用水热法分别生长出Mo S2纳米片和Ni Co2O4纳米针,用同样的方法在生长有Mo S2纳米片的不锈钢网上二次负载Ni Co2O4纳米针制得了Ni Co2O4/Mo S2复合结构。利用SEM、TEM及XRD等手段对复合结构的表面形貌和物相组成进行表征,通过电化学工作站测试材料的析氢性能。结果表明,Ni Co2O4/Mo S2复合结构表现最佳,在析氢反应过程中起始过电位仅为65 m V,Tafel斜率为108 m V/dec,当电流密度达到100 m A/cm2时,过电位仅219.6 m V,且循环稳定性良好。
文摘电解水技术是一种生产高纯氢燃料的方法,能够增强可再生能源发电系统的消纳能力.相较于质子交换膜(PEM)电解槽,碱性(ALK)电解槽可以使用非贵金属基催化电极,拥有更高的经济效益和市场占有率.然而,由于ALK电解槽处于质子稀缺环境,阴极氢气演化反应(HER)动力学变得更加复杂,需要快速解离水分子提供动态质子微环境.硫化钼(MoS_(2))纳米片边缘具有合适的质子吸附和演化的活性位点,是制备HER催化剂的潜力材料.但其二维基面原子由于配位饱和,显示出较弱的质子吸附能力.如何调控MoS_(2)基面以实现水解动力与质子吸附演化动力的集成,提升MoS_(2)纳米片的碱性HER活性,具有重要的科学和应用意义.本文提出了一种Co/O双原子植入策略,精准调控双活性位点及其电子结构,实现了水解离动力和质子吸附演化动力的高效耦联.首先,利用刻蚀和电沉积的两步实验法,在MoS_(2)基面上成功引入O和Co原子;随后,结合高分辨透射电镜、高角环形暗场-扫描透射电子显微镜、同步辐射X射线吸收精细结构谱等表征分析技术,精准识别了掺杂Co/O原子的位置和配位情况:O原子替换部分S原子,Co原子占据Mo原子的上方,构建出立体凸起的“O-Co-S_(2)”配位构型.催化在线的原位表征分析结果表明:该独特的“O-Co-S_(2)”原子基序发挥着水解离与氢演化反应协同催化效应.密度泛函理论计算结果也证实了该协同机制,其中Co位点促进水的解离反应,而S位点则有助于质子的转化生成氢气.因此,Co/O掺杂MoS_(2)催化剂(Co-O@MoS_(2))表现出较好的碱性HER活性:仅需81 mV的过电位,即可达到100 mA cm^(‒2)的电流密度,Tafel斜率低至42 mV dec^(‒1),在600 mA cm^(‒2)的高电流密度测试中运行300 h活性无衰减.上述碱性HER性能不仅远高于原始的MoS_(2)纳米片,而且也领先于部分已报道结果.综上所述,本文在MoS_(2)基面上构筑了原�
文摘A series of unsupported MoS2 catalysts with or without Al2O3 modification was prepared using a modified thermal decomposition approach. The catalysts were tested for the methanation of carbon monoxide and the optimum one has 25.6wt-% Al2O3 content. The catalysts were characterized by nitrogen adsorption measurement, X-ray diffraction and transmission electron microscopy. The results show that adding appropriate amount of Al2O3 increases the dispersion of MoS2, and the increased interaction force between MoS2 and Al2O3 can inhibit the sintering of active MoS2 to some extent.
