China is extremely poor in mineral resources of Platinum Group Metals (PGMs), productive output of PGMs from mineral resource is 2.5 tons per year. At the same time, China is the biggest PGMs consumption country in th...China is extremely poor in mineral resources of Platinum Group Metals (PGMs), productive output of PGMs from mineral resource is 2.5 tons per year. At the same time, China is the biggest PGMs consumption country in the world, the mineral resource of PGMs is critical shortage, it shows the importance of recycling the secondary resource of PGMs. Sino-Platinum Metals Resource (Yimen) Co., Ltd. is the leader in recycling of PGMs from secondary resource, and has made outstanding contributions to China PGMs secondary resources recycling. This article elucidates the current situation of secondary resources recovery and development of metallurgical technology for PGMs.展开更多
Platinum group metals (PGM) include six elements, namely Pt, Pd, Rh, Ir, Os and Ru. PGM and their alloys are the important fundamental materials for modern industry and national defense construction, they have special...Platinum group metals (PGM) include six elements, namely Pt, Pd, Rh, Ir, Os and Ru. PGM and their alloys are the important fundamental materials for modern industry and national defense construction, they have special physical and chemical properties, widely used in metallurgy, chemical, electric, electronic, information, energy, environmental protection, aviation, aerospace, navigation and other high technology industry. Platinum group metals and their alloys, which have good plasticity and processability, can be processed to electrical contact materials, resistance materials, solder, electronic paste, temperature-measurement materials, elastic materials, magnetic materials and high temperature structural materials.展开更多
Fe-N-doped carbon materials(Fe-N-C)are promising candidates for oxygen reduction reaction(ORR)relative to Pt-based catalysts in proton exchange membrane fuel cells(PEMFCs).However,the intrinsic contributions of Fe-N_(...Fe-N-doped carbon materials(Fe-N-C)are promising candidates for oxygen reduction reaction(ORR)relative to Pt-based catalysts in proton exchange membrane fuel cells(PEMFCs).However,the intrinsic contributions of Fe-N_(4)moiety with different chemical/spin states(e.g.D1,D2,D3)to ORR are unclear since various states coexist inevitably.In the present work,Fe-N-C core-shell nanocatalyst with single lowspin Fe(Ⅱ)-N_(4)species(D1)is synthesized and identified with ex-situ ultralow temperature Mossbauer spectroscopy(T=1.6 K)that could essentially differentiate various Fe-N_(4)states and invisible Fe-O species.By quantifying with CO-pulse chemisorption,site density and turnover frequency of Fe-N-C catalysts reach 2.4×10^(-9)site g^(-1)and 23 e site~(-1)s^(-1)during the ORR,respectively.Half-wave potential(0.915V_(RHE))of the Fe-N-C catalyst is more positive(approximately 54 mV)than that of Pt/C.Moreover,we observe that the performance of PEMFCs on Fe-N-C almost achieves the 2025 target of the US Department of Energy by demonstrating a current density of 1.037 A cm^(-2)combined with the peak power density of 0,685 W cm^(-2),suggesting the critical role of Fe(Ⅱ)-N_(4)site(D1).After 500 h of running,PEMFCs still deliver a power density of 1.26 W cm^(-2)at 1.0 bar H_(2)-O_(2),An unexpected rate-determining step is figured out by isotopic labelling experiment and theoretical calculation.This work not only offers valuable insights regarding the intrinsic contribution of Fe-N_(4)with a single spin state to alkaline/acidic ORR,but also provides great opportunities for developing high-performance stable PEMFCs.展开更多
Production of petrochemical catalysts accounts for one of the largest shares of platinum group metals(PGMs) consumption;thus,recycling of spent petrochemical catalysts holds great economic value.Conventionally,PGMs ar...Production of petrochemical catalysts accounts for one of the largest shares of platinum group metals(PGMs) consumption;thus,recycling of spent petrochemical catalysts holds great economic value.Conventionally,PGMs are recovered through hydrometallurgical processes which have a low recovery efficiency and produce a large amount of waste.In this regard,this paper proposed a method to use iron-capturing PGMs based on CaO-Al_(2)O_(3)-Na_(2)O slag.This method avoided the formation of Fe-Si alloy and achieved efficient enrichment of PGMs.The droplet force model showed that the recovery efficiency of PGMs could be improved if the slag had low density and low viscosity.Based on this result,FactSage software optimized the composition of slag.Furthermore,the effect of B_(2)O_(3) on the 1400 ℃ liquidus of CaO-Al_(2)O_(3)-Na_(2)O_(3)-B_(2)O_(3) phase diagram was revealed.Moreover,it was found that the recovery efficiency of PGMs exceeded 99% under the following optimized conditions:basicity of 1.0,20 wt%Na_(2)O,15 wt% B_(2)O_(3),15 wt% Fe,3 wt% C and a temperature range of 1400-1500℃.The thermodynamic model revealed the mechanism of iron capture.Different chemical bonds prevented the formation of bonds between the alloy and slag,resulting in the separation of the slag from the alloy.PGMs particles and iron microspheres had significant surface Gibbs free energy.Only when iron microspheres and PGMs particles collided and fused with each other to reduce their surface area could the Gibbs free energy of the system be reduced.展开更多
Platinum group metals(PGMs),especially Pd,Pt,and Rh,have drawn great attention due to their unique features.Direct separation of Pd and Pt from highly acidic automobile catalyst leach liquors is disturbed by various f...Platinum group metals(PGMs),especially Pd,Pt,and Rh,have drawn great attention due to their unique features.Direct separation of Pd and Pt from highly acidic automobile catalyst leach liquors is disturbed by various factors.This work investigates the effect of various parameters including the acidity,extractant concentration,phase ratio A/O,and diluents on the Pd and Pt extraction and their stripping behaviors.The results show that the Pd and Pt are successfully separated from simulated leach liquor of spent automobile catalysts with monothioCyanex 272 and trioctylamine(TOA).Monothio-Cyanex 272 shows strong extractability and specific selectivity for Pd,and only one single stage is needed to recover more than 99.9% of Pd,leaving behind all the Pt,Rh,and base metals of Fe,Mg,Ce,Ni,Cu,and Co in the raffinate.The loaded Pd is efficiently stripped by acidic thiourea solutions.TOA shows strong extractability for Pt and Fe at acidity of 6 mol·L^(–1) HCl.More than 99.9% of Pt and all of the Fe are extracted into the organic phase after two stages of countercurrent extraction.Diluted HCl easily scrubs the loaded base metals(Fe,Cu,and Co).The loaded Pt is efficiently stripped by 1.0 mol·L^(–1) thiourea and 0.05–0.1 mol·L^(–1) Na OH solutions.Monothio-Cyanex 272 and TOA can realize the separation of Pd and Pt from highly acidic leach liquor of spent automobile catalysts.展开更多
基金the National High Technology Research and Development Program of China(863 Program) (2012AA063203)Funded by Science and Technology Department of Yunnan Province (2011AA004)
文摘China is extremely poor in mineral resources of Platinum Group Metals (PGMs), productive output of PGMs from mineral resource is 2.5 tons per year. At the same time, China is the biggest PGMs consumption country in the world, the mineral resource of PGMs is critical shortage, it shows the importance of recycling the secondary resource of PGMs. Sino-Platinum Metals Resource (Yimen) Co., Ltd. is the leader in recycling of PGMs from secondary resource, and has made outstanding contributions to China PGMs secondary resources recycling. This article elucidates the current situation of secondary resources recovery and development of metallurgical technology for PGMs.
基金supported by the National Nature Science Foundation of China(No.u0837601)
文摘Platinum group metals (PGM) include six elements, namely Pt, Pd, Rh, Ir, Os and Ru. PGM and their alloys are the important fundamental materials for modern industry and national defense construction, they have special physical and chemical properties, widely used in metallurgy, chemical, electric, electronic, information, energy, environmental protection, aviation, aerospace, navigation and other high technology industry. Platinum group metals and their alloys, which have good plasticity and processability, can be processed to electrical contact materials, resistance materials, solder, electronic paste, temperature-measurement materials, elastic materials, magnetic materials and high temperature structural materials.
基金financial support from the“Hundred Talents Program”of the Chinese Academy of Sciencesthe“Young Talents Training Program”of the Shanghai Branch of the Chinese Academy of Sciences+3 种基金the financial support from the Xiamen City Natural Science Foundation of China(3502Z20227085,3502Z20227256)the National Science Youth Foundation of China(22202205)the Fujian Provincial Natural Science Foundation of China(2022J01502)Open Source Foundation of State Key Laboratory of Structural Chemistry。
文摘Fe-N-doped carbon materials(Fe-N-C)are promising candidates for oxygen reduction reaction(ORR)relative to Pt-based catalysts in proton exchange membrane fuel cells(PEMFCs).However,the intrinsic contributions of Fe-N_(4)moiety with different chemical/spin states(e.g.D1,D2,D3)to ORR are unclear since various states coexist inevitably.In the present work,Fe-N-C core-shell nanocatalyst with single lowspin Fe(Ⅱ)-N_(4)species(D1)is synthesized and identified with ex-situ ultralow temperature Mossbauer spectroscopy(T=1.6 K)that could essentially differentiate various Fe-N_(4)states and invisible Fe-O species.By quantifying with CO-pulse chemisorption,site density and turnover frequency of Fe-N-C catalysts reach 2.4×10^(-9)site g^(-1)and 23 e site~(-1)s^(-1)during the ORR,respectively.Half-wave potential(0.915V_(RHE))of the Fe-N-C catalyst is more positive(approximately 54 mV)than that of Pt/C.Moreover,we observe that the performance of PEMFCs on Fe-N-C almost achieves the 2025 target of the US Department of Energy by demonstrating a current density of 1.037 A cm^(-2)combined with the peak power density of 0,685 W cm^(-2),suggesting the critical role of Fe(Ⅱ)-N_(4)site(D1).After 500 h of running,PEMFCs still deliver a power density of 1.26 W cm^(-2)at 1.0 bar H_(2)-O_(2),An unexpected rate-determining step is figured out by isotopic labelling experiment and theoretical calculation.This work not only offers valuable insights regarding the intrinsic contribution of Fe-N_(4)with a single spin state to alkaline/acidic ORR,but also provides great opportunities for developing high-performance stable PEMFCs.
基金financially supported by the National Natural Science Foundation of China (Nos.U2002212 and 52204412)the National Key R&D Program of China (Nos. 2019YFC1907101,2019YFC1907103 and 2021YFC1910504)+3 种基金Key R&D Program of Ningxia Hui Autonomous Region (No. 2020BCE01001)Guangdong Basic and Applied Basic Research Foundation (No.2020A1515110408)Foshan Science and Technology Innovation Special Foundation (No.BK21BE002)the Fundamental Research Funds for the Central Universities (No.FRF-TP20-031A1)。
文摘Production of petrochemical catalysts accounts for one of the largest shares of platinum group metals(PGMs) consumption;thus,recycling of spent petrochemical catalysts holds great economic value.Conventionally,PGMs are recovered through hydrometallurgical processes which have a low recovery efficiency and produce a large amount of waste.In this regard,this paper proposed a method to use iron-capturing PGMs based on CaO-Al_(2)O_(3)-Na_(2)O slag.This method avoided the formation of Fe-Si alloy and achieved efficient enrichment of PGMs.The droplet force model showed that the recovery efficiency of PGMs could be improved if the slag had low density and low viscosity.Based on this result,FactSage software optimized the composition of slag.Furthermore,the effect of B_(2)O_(3) on the 1400 ℃ liquidus of CaO-Al_(2)O_(3)-Na_(2)O_(3)-B_(2)O_(3) phase diagram was revealed.Moreover,it was found that the recovery efficiency of PGMs exceeded 99% under the following optimized conditions:basicity of 1.0,20 wt%Na_(2)O,15 wt% B_(2)O_(3),15 wt% Fe,3 wt% C and a temperature range of 1400-1500℃.The thermodynamic model revealed the mechanism of iron capture.Different chemical bonds prevented the formation of bonds between the alloy and slag,resulting in the separation of the slag from the alloy.PGMs particles and iron microspheres had significant surface Gibbs free energy.Only when iron microspheres and PGMs particles collided and fused with each other to reduce their surface area could the Gibbs free energy of the system be reduced.
基金financially supported by the National Key Research and Development Program for Young Scientists,China(No.2021YFC2901100)。
文摘Platinum group metals(PGMs),especially Pd,Pt,and Rh,have drawn great attention due to their unique features.Direct separation of Pd and Pt from highly acidic automobile catalyst leach liquors is disturbed by various factors.This work investigates the effect of various parameters including the acidity,extractant concentration,phase ratio A/O,and diluents on the Pd and Pt extraction and their stripping behaviors.The results show that the Pd and Pt are successfully separated from simulated leach liquor of spent automobile catalysts with monothioCyanex 272 and trioctylamine(TOA).Monothio-Cyanex 272 shows strong extractability and specific selectivity for Pd,and only one single stage is needed to recover more than 99.9% of Pd,leaving behind all the Pt,Rh,and base metals of Fe,Mg,Ce,Ni,Cu,and Co in the raffinate.The loaded Pd is efficiently stripped by acidic thiourea solutions.TOA shows strong extractability for Pt and Fe at acidity of 6 mol·L^(–1) HCl.More than 99.9% of Pt and all of the Fe are extracted into the organic phase after two stages of countercurrent extraction.Diluted HCl easily scrubs the loaded base metals(Fe,Cu,and Co).The loaded Pt is efficiently stripped by 1.0 mol·L^(–1) thiourea and 0.05–0.1 mol·L^(–1) Na OH solutions.Monothio-Cyanex 272 and TOA can realize the separation of Pd and Pt from highly acidic leach liquor of spent automobile catalysts.
