Fe(Ⅲ)has been proved to be a more eff ective oxidant than dissolved oxygen at ambient temperature,however,the role of Fe(Ⅲ)in pyrite acidic pressure oxidation was rarely discussed so far.In this paper,in-situ electr...Fe(Ⅲ)has been proved to be a more eff ective oxidant than dissolved oxygen at ambient temperature,however,the role of Fe(Ⅲ)in pyrite acidic pressure oxidation was rarely discussed so far.In this paper,in-situ electrochemical investigation was performed using a flow-through autoclave system in acidic pressure oxidation environment.The results illustrated that increasing Fe(Ⅲ)concentrations led to raising in redox potential of the solution,and decreased passivation of pyrite caused by deposition of elemental sulfur.Reduction of Fe(Ⅲ)at pyrite surface was a fast reaction with low activation energy,it was only slightly promoted by rising temperatures.While,the oxidation rate of pyrite at all investigated Fe(Ⅲ)concentrations increased obviously with rising temperatures,the anodic reaction was the rate-limiting step in the overall reaction.Activation energy of pyrite oxidation decreased from 47.74 to 28.79 kJ/mol when Fe(Ⅲ)concentration was increased from 0.05 to 0.50 g/L,showing that the reaction kinetics were limited by the rate of electrochemical reaction at low Fe(Ⅲ)concentrations,while,it gradually turned to be diffusion control with increasing Fe(Ⅲ)concentrations.展开更多
A new copper-thiolate cluster assembled framework[Cu2(μ4-SCH3)Cl]n(1),has been solvothermally synthesized through in situ reaction viz.,in situ ligand generation and metal reduction.Compound 1 represents the first 3 ...A new copper-thiolate cluster assembled framework[Cu2(μ4-SCH3)Cl]n(1),has been solvothermally synthesized through in situ reaction viz.,in situ ligand generation and metal reduction.Compound 1 represents the first 3 D framework based on Atlas-sphere functionalized by singleμ2-Cl groups.DOS calculation reveals the interaction of electronic structures.It is found that the HOMO is mainly distributed on Cl,Cu and S bonding orbitals,while the LUMO is dominated by Cu-Cl antibonding orbitals.展开更多
基金supported by the Science and Technology Foundation of Guizhou Province,China(No.[2020]1Y163)the National Natural Science Foundation of China(No.41827802).
文摘Fe(Ⅲ)has been proved to be a more eff ective oxidant than dissolved oxygen at ambient temperature,however,the role of Fe(Ⅲ)in pyrite acidic pressure oxidation was rarely discussed so far.In this paper,in-situ electrochemical investigation was performed using a flow-through autoclave system in acidic pressure oxidation environment.The results illustrated that increasing Fe(Ⅲ)concentrations led to raising in redox potential of the solution,and decreased passivation of pyrite caused by deposition of elemental sulfur.Reduction of Fe(Ⅲ)at pyrite surface was a fast reaction with low activation energy,it was only slightly promoted by rising temperatures.While,the oxidation rate of pyrite at all investigated Fe(Ⅲ)concentrations increased obviously with rising temperatures,the anodic reaction was the rate-limiting step in the overall reaction.Activation energy of pyrite oxidation decreased from 47.74 to 28.79 kJ/mol when Fe(Ⅲ)concentration was increased from 0.05 to 0.50 g/L,showing that the reaction kinetics were limited by the rate of electrochemical reaction at low Fe(Ⅲ)concentrations,while,it gradually turned to be diffusion control with increasing Fe(Ⅲ)concentrations.
基金the National Natural Science Foundation of China(Nos.21861012 and 21603109)the Henan Joint Fund of the National Natural Science Foundation of China(No.U1404216)+6 种基金the Natural Science Foundation of Guizhou Education Commission(Nos.2018148 and 2018016)Guizhou Science&Technology Commission(Nos.20201Z005,20191157 and 20191156)the Natural Science Foundation of Shandong Provinceof China(No.ZR2016BM14)Tai’an Science&Technology Project(No.2016GX1046)the Postgraduate Foundation of Taishan University(No.Y2015-1-011)the Natural Science Foundation of Guizhou Minzu University(No.GZMU2019YB06)the Natural Science Foundation of Liaoning Shihua University(No.2019XJJL019)。
文摘A new copper-thiolate cluster assembled framework[Cu2(μ4-SCH3)Cl]n(1),has been solvothermally synthesized through in situ reaction viz.,in situ ligand generation and metal reduction.Compound 1 represents the first 3 D framework based on Atlas-sphere functionalized by singleμ2-Cl groups.DOS calculation reveals the interaction of electronic structures.It is found that the HOMO is mainly distributed on Cl,Cu and S bonding orbitals,while the LUMO is dominated by Cu-Cl antibonding orbitals.