金属-硫脲配合物的结构复杂,种类繁多,为了解决其由于缺少热力学数据难以进行热力学分析的问题,将金属-硫脲配合物看成由简单有机物和离子组成,采用PeHbo方程、Misenrd估算法和D. F. Taylor法分别计算金属-硫脲配合物和简单有机物及离...金属-硫脲配合物的结构复杂,种类繁多,为了解决其由于缺少热力学数据难以进行热力学分析的问题,将金属-硫脲配合物看成由简单有机物和离子组成,采用PeHbo方程、Misenrd估算法和D. F. Taylor法分别计算金属-硫脲配合物和简单有机物及离子的标准摩尔热容.利用гepцa方程计算金属-硫脲配合物的标准摩尔生成熵,根据简单有机物和离子的标准摩尔生成焓和计算得到的标准摩尔生成熵,计算金属-硫脲配合物的标准摩尔生成自由能.通过对金属-硫脲配合物热力学数据的估算,为实现热力学分析在金属-硫脲配合物中的应用提供理论基础.展开更多
Increasing interest has been paid to the development of earth‐abundant metal complexes as promising surrogates of platinum for the electrocatalytically and photocatalytically driven hydrogen evolution reaction.In thi...Increasing interest has been paid to the development of earth‐abundant metal complexes as promising surrogates of platinum for the electrocatalytically and photocatalytically driven hydrogen evolution reaction.In this work,we report on molecular H2‐evolving catalysts based on two octahedral complexes of cobalt thiosemicarbazide,fac‐[Co(Htsc)3]Cl3·3H2O(C1,Htsc=thiosemicarbazide)and mer‐[Co(Htsc)3]Cl3·4H2O(C2),which have facial(fac)and meridional(mer)geometry,respectively.Electrochemical studies confirmed that both C1and C2are active electrocatalysts in MeOH solution using acetic acid as the proton source,with the same overpotential of^640mV and TOF of^210s–1.The complex C1also exhibits electrocatalytic activity for hydrogen evolution reaction in aqueous media free of organic solvent with a moderate overpotential(560mV).Visible light‐driven hydrogen evolution experiments were carried out in combination with fluorescein as photosensitizer and triethylamine as sacrificial reductant in homogeneous environments.Our studies showed that both C1and C2can be used as efficient proton‐reduction catalysts in purely aqueous solution and have the same photocatalytic activities.A TOF of125h–1with a TON of900for photocatalytic H2generation using C1and C2in water were achieved for the noble‐metal‐free homogeneous system.It should be noted that this is the first reported study investigating the effect on the catalytic hydrogen production performance of using fac‐and mer‐isomers of molecular catalysts.展开更多
文摘金属-硫脲配合物的结构复杂,种类繁多,为了解决其由于缺少热力学数据难以进行热力学分析的问题,将金属-硫脲配合物看成由简单有机物和离子组成,采用PeHbo方程、Misenrd估算法和D. F. Taylor法分别计算金属-硫脲配合物和简单有机物及离子的标准摩尔热容.利用гepцa方程计算金属-硫脲配合物的标准摩尔生成熵,根据简单有机物和离子的标准摩尔生成焓和计算得到的标准摩尔生成熵,计算金属-硫脲配合物的标准摩尔生成自由能.通过对金属-硫脲配合物热力学数据的估算,为实现热力学分析在金属-硫脲配合物中的应用提供理论基础.
基金supported by the National Natural Science Foundation of China (21641011, 21773313)the Natural Science Foundation of Fujian Province (2015J01053, 2016J01060)+1 种基金Program for New Century Excellent Talents in Fujian Province UniversityPromotion Program for Young and Middle-aged Teacher in Science, Technology Research of Huaqiao University (ZQN-PY104)~~
文摘Increasing interest has been paid to the development of earth‐abundant metal complexes as promising surrogates of platinum for the electrocatalytically and photocatalytically driven hydrogen evolution reaction.In this work,we report on molecular H2‐evolving catalysts based on two octahedral complexes of cobalt thiosemicarbazide,fac‐[Co(Htsc)3]Cl3·3H2O(C1,Htsc=thiosemicarbazide)and mer‐[Co(Htsc)3]Cl3·4H2O(C2),which have facial(fac)and meridional(mer)geometry,respectively.Electrochemical studies confirmed that both C1and C2are active electrocatalysts in MeOH solution using acetic acid as the proton source,with the same overpotential of^640mV and TOF of^210s–1.The complex C1also exhibits electrocatalytic activity for hydrogen evolution reaction in aqueous media free of organic solvent with a moderate overpotential(560mV).Visible light‐driven hydrogen evolution experiments were carried out in combination with fluorescein as photosensitizer and triethylamine as sacrificial reductant in homogeneous environments.Our studies showed that both C1and C2can be used as efficient proton‐reduction catalysts in purely aqueous solution and have the same photocatalytic activities.A TOF of125h–1with a TON of900for photocatalytic H2generation using C1and C2in water were achieved for the noble‐metal‐free homogeneous system.It should be noted that this is the first reported study investigating the effect on the catalytic hydrogen production performance of using fac‐and mer‐isomers of molecular catalysts.
