Direct recycling has been regarded as one of the most promising approaches to dealing with the increasing amount of spent lithium‐ion batteries(LIBs).However,the current direct recycling method remains insufficient t...Direct recycling has been regarded as one of the most promising approaches to dealing with the increasing amount of spent lithium‐ion batteries(LIBs).However,the current direct recycling method remains insufficient to regenerate outdated cathodes to meet current industry needs as it only aims at recovering the structure and composition of degraded cathodes.Herein,a nickel(Ni)and manganese(Mn)co‐doping strategy has been adopted to enhance LiCoO_(2)(LCO)cathode for next‐generation high‐performance LIBs through a conventional hydrothermal treatment combined with short annealing approach.Unlike direct recycling methods that make no changes to the chemical composition of cathodes,the unique upcycling process fabricates a series of cathodes doped with different contents of Ni and Mn.The regenerated LCO cathode with 5%doping delivers excellent electrochemical performance with a discharge capacity of 160.23 mAh g^(−1) at 1.0 C and capacity retention of 91.2%after 100 cycles,considerably surpassing those of the pristine one(124.05 mAh g^(−1) and 89.05%).All results indicate the feasibility of such Ni–Mn co‐doping‐enabled upcycling on regenerating LCO cathodes.展开更多
Pollution of marine environment has become an issue of major concern in recent years. Serious environmental pollution by heavy metals results from their increasing utilization in industrial processes and because most ...Pollution of marine environment has become an issue of major concern in recent years. Serious environmental pollution by heavy metals results from their increasing utilization in industrial processes and because most heavy metals are transported into the marine environment and accumulated without decomposition. The aim of the present study is to investigate the effects on growth, pigments, lipid peroxidation, and some antioxidant enzyme activities of marine microalga Pavlova viridis, in response to elevated concentrations of cobalt （Co） and manganese （Mn）, especially with regard to the involvement of antioxidative defences against heavy metal-induced oxidative stress. In response to Co^2＋, lipid peroxidation was enhanced compared to the control, as an indication of the oxidative damage caused by metal concentration assayed in the microalgal cells but not Mn^2＋. Exposure of Pavlova viridis to the two metals caused changes in enzyme activities in a different manner, depending on the metal assayed： after Co^2＋ treatments, total superoxide dismutase （SOD） activity was irregular, although it was not significantly affected by Mn^2＋ exposure. Co^2＋ and Mn^2＋ stimulated the activities of catalase （CAT） and glutathione （GSH）, whereas, glutathione peroxidase （GPX） showed a remarkable increase in activity in response to Co^2＋ treatments and decreased gradually with Mn^2＋ concentration, up to 50 μmol/L, and then rose very rapidly, reaching to about 38.98% at 200 μmol/L Mn^2＋. These results suggest that an activation of some antioxidant enzymes was enhanced, to counteract the oxidative stress induced by the two metals at higher concentration.展开更多
We demonstrate a novel preparative strategy for the well-controlled MnCo_2O_(4.5)@MnO_2 hierarchical nanostructures.Bothδ-MnO_2 nanosheets andα-MnO_2 nanorods can uniformly decorate the surface of MnCo_2O_(4.5)nanow...We demonstrate a novel preparative strategy for the well-controlled MnCo_2O_(4.5)@MnO_2 hierarchical nanostructures.Bothδ-MnO_2 nanosheets andα-MnO_2 nanorods can uniformly decorate the surface of MnCo_2O_(4.5)nanowires to form core-shell heterostructures.Detailed electrochemical characterization reveals that MnCo_2O_(4.5)@δ-MnO_2 pattern exhibits not only high specific capacitance of 357.5 F g^(-1)at a scan rate of 0.5 A g^(-1),but also good cycle stability(97%capacitance retention after 1000 cycles at a scan rate of 5 A g^(-1)),which make it have a promising application as a supercapacitor electrode material.展开更多
The exploration of low-cost and efficient bifunctional electrocatalysts for oxygen evolution reaction and hydrogen evolution reaction through tuning the chemical composition is strongly required for sustainable resour...The exploration of low-cost and efficient bifunctional electrocatalysts for oxygen evolution reaction and hydrogen evolution reaction through tuning the chemical composition is strongly required for sustainable resources. Herein, we developed a bimetallic cobalt–manganese sulfide supported on Ni foam(CMS/Ni) via a solvothermal method. It has discovered that after combining with the pure Co_9S_8 and Mn S, the morphologies of CMS/Ni have modulated. The obtained three-dimensionally hexagram-like CMS/Ni nanosheets have a significant increase in electrochemical active surface area and charge transport ability. More than that, the synergetic effect of Co and Mn has also presented in this composite. Benefiting from these, the CMS/Ni electrode shows great performance toward hydrogen evolution reaction and oxygen evolution reaction in basic medium, comparing favorably to that ofthe pure Co_9S_8/Ni and Mn S/Ni. More importantly, this versatile CMS/Ni can catalyze the water splitting in a twoelectrode system at a potential of 1.47 V, and this electrolyzer can be efficiently driven by a 1.50 V commercial dry battery.展开更多
Two complexes with a zwitterionic dicarboxylate ligand,Mn（L）2（H2O）4 1 and Co（L）2（H2O）4 2（L = 1-carboxymethylpyridinium-4-carboxylate）,were synthesized and structurally characterized.Complex 1 crystallizes in...Two complexes with a zwitterionic dicarboxylate ligand,Mn（L）2（H2O）4 1 and Co（L）2（H2O）4 2（L = 1-carboxymethylpyridinium-4-carboxylate）,were synthesized and structurally characterized.Complex 1 crystallizes in monoclinic,space group P21 with a = 6.490（2）,b = 19.210（7）,c = 7.813（3） ,β = 92.716（5）o,V = 972.9（6） 3,Z = 2,Mr = 487.28,Dc = 1.663 g/cm3,F（000） = 502,μ = 0.749 mm-1,S = 1.060,the final R = 0.0377 and wR = 0.0893 for 3292 observed reflections with I 2σ（I）.Complex 2 is isomorphous with 1,with a = 6.478（2）,b = 19.052（7）,c = 7.742（3） ,β = 92.690（4）o,V = 954.6（6） 3,Z = 2,Mr = 491.28,Dc = 1.709 g/cm3,F（000） = 506,μ = 0.971 mm-1,S = 1.035,the final R = 0.0425 and wR = 0.0809 for 3289 observed reflections with I 2σ（I）.In the compounds,the mononuclear [M（L）2（H2O）4] units with trans-octahedral coordination geometry are linked into 3D architectures via hydrogen bonding（or second-sphere coordination） involving carboxylate groups and coordinated water molecules.The 3D networks illustrate a 3,8-connected net with Schlfli symbol（4·62）2（42·623·83）.展开更多
In Fischer-Tropsch synthesis reaction, methane formation is one of the side reactions which must be suppressed in order to get better catalytic selectivity for light olefins. In the present study, we have modified cob...In Fischer-Tropsch synthesis reaction, methane formation is one of the side reactions which must be suppressed in order to get better catalytic selectivity for light olefins. In the present study, we have modified cobalt based Fischer-Tropsch catalyst and developed a process to minimize methane production, consequently to produce maximum yield of light olefins. Manganese-cobalt oxide supported on H-5A zeolite catalyst was synthesized using modified H-5A zeolite, to increase its surface acid sites. Increased acidity of zeolite plays a major part in the suppression of methane formation during the Fischer-Tropsch reaction. The modified zeolite results in the electronic modification of catalyst surface by creating new active catalytic sites. The results are compared with other supported catalysts along with unmodified zeolite. Appreciable reduction in methane formation is achieved on modified zeolite supported catalyst in comparison with unsupported catalyst.展开更多
The recovery of Mn, Co and Ni from deep-sea manganese nodules was conducted by acid oxidative leaching and solvent extraction. The results indicate that pyrrhotite used during leaching can effectively facilitate the l...The recovery of Mn, Co and Ni from deep-sea manganese nodules was conducted by acid oxidative leaching and solvent extraction. The results indicate that pyrrhotite used during leaching can effectively facilitate the leaching out of manganese, cobalt and nickel. The leaching behaviors of Mn, Ni and Co were determined and the influences of temperature, leaching time and sulphuric acid concentration on leaching rate were also investigated. Co and Ni are precipitated from the leaching liquor by adding sodium sulfide into solution with agitation for 2 h at 50 ℃, and the manganese sulphate is obtained by concentrating the resulting solution. By re-dissolving the precipitates of cobalt and nickel, the separation of cobalt and nickel is performed using di(2-ethylhexyl) phosphoric acid (D2EHPA) for impurities elimination with 8 stages at organic-to-aqueous(O/A) volume ratio of 3:5, and 2- ethylhexyl phosphonic acid mono-2-ethylhexyl ester (known as PC88A or P507) for cobalt extraction with 3 stages counter-current operations at O/A volume ratio of 2:3 followed by their scrubbings and strippings, respectively. The final maximum recovery rates for manganese, cobalt and nickel are 85%, 75% and 78%, respectively.展开更多
China’s manganese resources are usually associated with the valuable elements such as silver, lead, zinc, cobalt, nickel, scandium, etc which should be comprehensively recovered during the manganese beneficiation. A ...China’s manganese resources are usually associated with the valuable elements such as silver, lead, zinc, cobalt, nickel, scandium, etc which should be comprehensively recovered during the manganese beneficiation. A manganese ore from western China contains Mn 23.18%, Co 0.073%, Ni 0.21% and Sc 0.013%. The mineralogy composition of ore and the occurrence of associated elements of Sc, Co as well as Ni are studied in this paper. According to the results, the manganese minerals in this ore are mainly lithiophorite and a little secondary pyrolusite. The lithiophorite in this ore is rich in aluminum and actually it is the generic name for the multi-mineral aggregates mixed by silicon, aluminum and iron, which is quite different with the ordinary psilomelane. There is not any Sc, Ni or Co mineral in this ore and more than 98% of Sc, Ni and Ni exists in lithiophorite and pyrolusite. The distribution of Sc, Co and Ni in lithiophorite is further studied by EPMA and the results indicate that Sc and Co in lithiophorite is sparse and dispersed distribution while Ni usually distributes in the argillaceous lithiophorite and is local enrichment. Reduction-sulfuric acid leaching tests show that the dissolution of Sc and Co happens before lithiophorite dissolves; the dissolution rate of Sc and Co is almost the same, which is significantly higher than the dissolution rate of manganese. However, the dissolution rate of Ni is extremely low with the dissolution of manganse, which indicates that Ni is hard to dissolve and its dissolution rate obviously lags behind that of Mn, Sc and Co. The conclusion can be drawn that Sc and Co exist in the lithiophorite crystals as interface adsorption while Ni exists in the clay (kaolinite) mixed up with lithiophorite as interface adsorption. The conclusion indicates that Sc and Co can dissolve before the dissolution of manganese at a high dissolution rate in the hydrometallurgical process while Ni is also into the solution through desorption from the interface of clay but its dissolution rate is rather slow because of the insoluble nature of clay.展开更多
The long-range periodically ordered atomic structures in intermetallic nanoparticles(INPs)can significantly enhance both the electrocatalytic activity and electrochemical stability toward the oxygen reduction reaction...The long-range periodically ordered atomic structures in intermetallic nanoparticles(INPs)can significantly enhance both the electrocatalytic activity and electrochemical stability toward the oxygen reduction reaction(ORR)compared to the disordered atomic structures in ordinary solid-solution alloy NPs.Accordingly,through a facile and scalable synthetic method,a series of carbon-supported ultrafine Pt_3Co_(x)Mn_(1-x)ternary INPs are prepared in this work,which possess the"skin-like"ultrathin Pt shells,the ordered L1_(2) atomic structure,and the high-even dispersion on supports(L1_(2)-Pt_3Co_(x)Mn_(1-x)/~SPt INPs/C).Electrochemical results present that the composition-optimized L1_(2)-Pt_3Co_(0.7)Mn_(0.3)/~SPt INPs/C exhibits the highest electrocata lytic activity among the series,which are also much better than those of the pristine ultrafine Pt/C.Besides,it also has a greatly enhanced electrochemical stability.In addition,the effects of annealing temperature and time are further investigated.More importantly,such superior ORR electrocatalytic performance of L1_(2)-Pt_3Co_(0.7)Mn_(0.3)/~SPt INPs/C are also well demonstrated in practical fuel cells.Physicochemical characterization analyses further reveal the major origins of the greatly enhanced ORR electrocata lytic performance:the Pt-Co-Mn alloy-induced geometric and ligand effects as well as the extremely high L1_(2) atomic-ordering degree.This work not only successfully develops a highly active and stable ordered ternary intermetallic ORR electrocatalyst,but also elucidates the corresponding"structure-function"relationship,which can be further applied in designing other intermetallic(electro)catalysts.展开更多
The cryptomelane-type manganese oxide (OMS-2)-supported Co (x Co/OMS-2;x=5,10,and15 wt.%) catalysts were prepared via a pre-incorporation route.The as-prepared materials were used as catalysts for catalytic oxidation ...The cryptomelane-type manganese oxide (OMS-2)-supported Co (x Co/OMS-2;x=5,10,and15 wt.%) catalysts were prepared via a pre-incorporation route.The as-prepared materials were used as catalysts for catalytic oxidation of toluene (2000 ppmV).Physical and chemical properties of the catalysts were measured using the X-ray diffraction (XRD),Fourier transform infrared spectroscopic (FT-IR),scanning electron microscopic (SEM),X-ray photoelectron spectroscopy (XPS),and hydrogen temperature-programmed reduction (H_(2)-TPR)techniques.Among all of the catalysts,10Co/OMS-2 performed the best,with the T90%,specific reaction rate at 245℃,and turnover frequency at 245℃ (TOFCo) being 245℃,1.23×10^(-3)moltoluene/(gcat·sec),and 11.58×10^(-3)sec-1for toluene oxidation at a space velocity of 60,000mL/(g·hr),respectively.The excellent catalytic performance of 10Co/OMS-2 were due to more oxygen vacancies,enhanced redox ability and oxygen mobility,and strong synergistic effect between Co species and OMS-2 support.Moreover,in the presence of poisoning gases CO_(2),SO_(2)or NH_(3),the activity of 10Co/OMS-2 decreased for the carbonate,sulfate and ammonia species covered the active sites and oxygen vacancies,respectively.After the activation treatment,the catalytic activity was partly recovered.The good low-temperature reducibility of 10Co/OMS-2 could also facilitate the redox process accompanied by the consecutive electron transfer between the adsorbed O_(2)and the cobalt or manganese ions.In the oxidation process of toluene,the benzoic and aldehydic intermediates werefirst generated,which were further oxidized to the benzoate intermediate that were eventually converted into H_(2)O and CO_(2).展开更多
基金support of NanoFAB in Electron Microscopy and FIB sample preparation at the University of Alberta in Canadasupported by the Natural Sciences and Engineering Research Council of Canada(NSERC)+3 种基金through the Discovery Grant Program(RGPIN-2018-06725)the Discovery Accelerator Supplement Grant program(RGPAS-2018-522651)by the New Frontiers in Research Fund-Exploration program(NFRFE-2019-00488)financial support from the University of Alberta and Future Energy Systems(FES-T06-Q03).
文摘Direct recycling has been regarded as one of the most promising approaches to dealing with the increasing amount of spent lithium‐ion batteries(LIBs).However,the current direct recycling method remains insufficient to regenerate outdated cathodes to meet current industry needs as it only aims at recovering the structure and composition of degraded cathodes.Herein,a nickel(Ni)and manganese(Mn)co‐doping strategy has been adopted to enhance LiCoO_(2)(LCO)cathode for next‐generation high‐performance LIBs through a conventional hydrothermal treatment combined with short annealing approach.Unlike direct recycling methods that make no changes to the chemical composition of cathodes,the unique upcycling process fabricates a series of cathodes doped with different contents of Ni and Mn.The regenerated LCO cathode with 5%doping delivers excellent electrochemical performance with a discharge capacity of 160.23 mAh g^(−1) at 1.0 C and capacity retention of 91.2%after 100 cycles,considerably surpassing those of the pristine one(124.05 mAh g^(−1) and 89.05%).All results indicate the feasibility of such Ni–Mn co‐doping‐enabled upcycling on regenerating LCO cathodes.
基金Project supported by the Natural Science Foundation of Jiangsu Province(No.95021301)China Postdoctoral Science Foundation(No.2005037121)Jiangsu Planned Projects for Postdoctoral Research Funds(No.0401001C)
文摘Pollution of marine environment has become an issue of major concern in recent years. Serious environmental pollution by heavy metals results from their increasing utilization in industrial processes and because most heavy metals are transported into the marine environment and accumulated without decomposition. The aim of the present study is to investigate the effects on growth, pigments, lipid peroxidation, and some antioxidant enzyme activities of marine microalga Pavlova viridis, in response to elevated concentrations of cobalt （Co） and manganese （Mn）, especially with regard to the involvement of antioxidative defences against heavy metal-induced oxidative stress. In response to Co^2＋, lipid peroxidation was enhanced compared to the control, as an indication of the oxidative damage caused by metal concentration assayed in the microalgal cells but not Mn^2＋. Exposure of Pavlova viridis to the two metals caused changes in enzyme activities in a different manner, depending on the metal assayed： after Co^2＋ treatments, total superoxide dismutase （SOD） activity was irregular, although it was not significantly affected by Mn^2＋ exposure. Co^2＋ and Mn^2＋ stimulated the activities of catalase （CAT） and glutathione （GSH）, whereas, glutathione peroxidase （GPX） showed a remarkable increase in activity in response to Co^2＋ treatments and decreased gradually with Mn^2＋ concentration, up to 50 μmol/L, and then rose very rapidly, reaching to about 38.98% at 200 μmol/L Mn^2＋. These results suggest that an activation of some antioxidant enzymes was enhanced, to counteract the oxidative stress induced by the two metals at higher concentration.
基金financial supports provided by National Natural Science Foundation of China(Grant no.51104194 and 51104121)International S&T Cooperation Projects of Chongqing(CSTC 2013 gjhz90001)+1 种基金National Key laboratory of Fundamental Science of Micro/Nano-device and System Technology(2013MS06,Chongqing University)State Education Ministry and Fundamental Research Funds for the Central Universities(Project no.CDJZR14135501 and CDJZR13130036,Chongqing University,PR China)
文摘We demonstrate a novel preparative strategy for the well-controlled MnCo_2O_(4.5)@MnO_2 hierarchical nanostructures.Bothδ-MnO_2 nanosheets andα-MnO_2 nanorods can uniformly decorate the surface of MnCo_2O_(4.5)nanowires to form core-shell heterostructures.Detailed electrochemical characterization reveals that MnCo_2O_(4.5)@δ-MnO_2 pattern exhibits not only high specific capacitance of 357.5 F g^(-1)at a scan rate of 0.5 A g^(-1),but also good cycle stability(97%capacitance retention after 1000 cycles at a scan rate of 5 A g^(-1)),which make it have a promising application as a supercapacitor electrode material.
基金supported by National Natural Science Foundation of China(21576113 and 21376105)Foshan Innovative and Entrepreneurial Research Team Program(No.2014IT100062)
文摘The exploration of low-cost and efficient bifunctional electrocatalysts for oxygen evolution reaction and hydrogen evolution reaction through tuning the chemical composition is strongly required for sustainable resources. Herein, we developed a bimetallic cobalt–manganese sulfide supported on Ni foam(CMS/Ni) via a solvothermal method. It has discovered that after combining with the pure Co_9S_8 and Mn S, the morphologies of CMS/Ni have modulated. The obtained three-dimensionally hexagram-like CMS/Ni nanosheets have a significant increase in electrochemical active surface area and charge transport ability. More than that, the synergetic effect of Co and Mn has also presented in this composite. Benefiting from these, the CMS/Ni electrode shows great performance toward hydrogen evolution reaction and oxygen evolution reaction in basic medium, comparing favorably to that ofthe pure Co_9S_8/Ni and Mn S/Ni. More importantly, this versatile CMS/Ni can catalyze the water splitting in a twoelectrode system at a potential of 1.47 V, and this electrolyzer can be efficiently driven by a 1.50 V commercial dry battery.
基金Supported by NNSFC (20771038)Shanghai Leading Academic Discipline Project (B409)
文摘Two complexes with a zwitterionic dicarboxylate ligand,Mn（L）2（H2O）4 1 and Co（L）2（H2O）4 2（L = 1-carboxymethylpyridinium-4-carboxylate）,were synthesized and structurally characterized.Complex 1 crystallizes in monoclinic,space group P21 with a = 6.490（2）,b = 19.210（7）,c = 7.813（3） ,β = 92.716（5）o,V = 972.9（6） 3,Z = 2,Mr = 487.28,Dc = 1.663 g/cm3,F（000） = 502,μ = 0.749 mm-1,S = 1.060,the final R = 0.0377 and wR = 0.0893 for 3292 observed reflections with I 2σ（I）.Complex 2 is isomorphous with 1,with a = 6.478（2）,b = 19.052（7）,c = 7.742（3） ,β = 92.690（4）o,V = 954.6（6） 3,Z = 2,Mr = 491.28,Dc = 1.709 g/cm3,F（000） = 506,μ = 0.971 mm-1,S = 1.035,the final R = 0.0425 and wR = 0.0809 for 3289 observed reflections with I 2σ（I）.In the compounds,the mononuclear [M（L）2（H2O）4] units with trans-octahedral coordination geometry are linked into 3D architectures via hydrogen bonding（or second-sphere coordination） involving carboxylate groups and coordinated water molecules.The 3D networks illustrate a 3,8-connected net with Schlfli symbol（4·62）2（42·623·83）.
文摘In Fischer-Tropsch synthesis reaction, methane formation is one of the side reactions which must be suppressed in order to get better catalytic selectivity for light olefins. In the present study, we have modified cobalt based Fischer-Tropsch catalyst and developed a process to minimize methane production, consequently to produce maximum yield of light olefins. Manganese-cobalt oxide supported on H-5A zeolite catalyst was synthesized using modified H-5A zeolite, to increase its surface acid sites. Increased acidity of zeolite plays a major part in the suppression of methane formation during the Fischer-Tropsch reaction. The modified zeolite results in the electronic modification of catalyst surface by creating new active catalytic sites. The results are compared with other supported catalysts along with unmodified zeolite. Appreciable reduction in methane formation is achieved on modified zeolite supported catalyst in comparison with unsupported catalyst.
文摘The recovery of Mn, Co and Ni from deep-sea manganese nodules was conducted by acid oxidative leaching and solvent extraction. The results indicate that pyrrhotite used during leaching can effectively facilitate the leaching out of manganese, cobalt and nickel. The leaching behaviors of Mn, Ni and Co were determined and the influences of temperature, leaching time and sulphuric acid concentration on leaching rate were also investigated. Co and Ni are precipitated from the leaching liquor by adding sodium sulfide into solution with agitation for 2 h at 50 ℃, and the manganese sulphate is obtained by concentrating the resulting solution. By re-dissolving the precipitates of cobalt and nickel, the separation of cobalt and nickel is performed using di(2-ethylhexyl) phosphoric acid (D2EHPA) for impurities elimination with 8 stages at organic-to-aqueous(O/A) volume ratio of 3:5, and 2- ethylhexyl phosphonic acid mono-2-ethylhexyl ester (known as PC88A or P507) for cobalt extraction with 3 stages counter-current operations at O/A volume ratio of 2:3 followed by their scrubbings and strippings, respectively. The final maximum recovery rates for manganese, cobalt and nickel are 85%, 75% and 78%, respectively.
文摘China’s manganese resources are usually associated with the valuable elements such as silver, lead, zinc, cobalt, nickel, scandium, etc which should be comprehensively recovered during the manganese beneficiation. A manganese ore from western China contains Mn 23.18%, Co 0.073%, Ni 0.21% and Sc 0.013%. The mineralogy composition of ore and the occurrence of associated elements of Sc, Co as well as Ni are studied in this paper. According to the results, the manganese minerals in this ore are mainly lithiophorite and a little secondary pyrolusite. The lithiophorite in this ore is rich in aluminum and actually it is the generic name for the multi-mineral aggregates mixed by silicon, aluminum and iron, which is quite different with the ordinary psilomelane. There is not any Sc, Ni or Co mineral in this ore and more than 98% of Sc, Ni and Ni exists in lithiophorite and pyrolusite. The distribution of Sc, Co and Ni in lithiophorite is further studied by EPMA and the results indicate that Sc and Co in lithiophorite is sparse and dispersed distribution while Ni usually distributes in the argillaceous lithiophorite and is local enrichment. Reduction-sulfuric acid leaching tests show that the dissolution of Sc and Co happens before lithiophorite dissolves; the dissolution rate of Sc and Co is almost the same, which is significantly higher than the dissolution rate of manganese. However, the dissolution rate of Ni is extremely low with the dissolution of manganse, which indicates that Ni is hard to dissolve and its dissolution rate obviously lags behind that of Mn, Sc and Co. The conclusion can be drawn that Sc and Co exist in the lithiophorite crystals as interface adsorption while Ni exists in the clay (kaolinite) mixed up with lithiophorite as interface adsorption. The conclusion indicates that Sc and Co can dissolve before the dissolution of manganese at a high dissolution rate in the hydrometallurgical process while Ni is also into the solution through desorption from the interface of clay but its dissolution rate is rather slow because of the insoluble nature of clay.
基金supported by the National Natural Science Foundation of China (No. U2033204)Engineering Laboratory of Battery Safety and Accident Control of Petroleum and Chemical Industry, China (No. ELBSAC202304)supported by Youth Innovation Promotion Association, Chinese Academy of Sciences (No. Y201768)
基金supported by the National Key Research and Development Program of China(2021YFB4001301)the Science and Technology Commission of Shanghai Municipality(21DZ1208600)the Oceanic Interdisciplinary Program of Shanghai Jiao Tong University(SL2021ZD105)。
文摘The long-range periodically ordered atomic structures in intermetallic nanoparticles(INPs)can significantly enhance both the electrocatalytic activity and electrochemical stability toward the oxygen reduction reaction(ORR)compared to the disordered atomic structures in ordinary solid-solution alloy NPs.Accordingly,through a facile and scalable synthetic method,a series of carbon-supported ultrafine Pt_3Co_(x)Mn_(1-x)ternary INPs are prepared in this work,which possess the"skin-like"ultrathin Pt shells,the ordered L1_(2) atomic structure,and the high-even dispersion on supports(L1_(2)-Pt_3Co_(x)Mn_(1-x)/~SPt INPs/C).Electrochemical results present that the composition-optimized L1_(2)-Pt_3Co_(0.7)Mn_(0.3)/~SPt INPs/C exhibits the highest electrocata lytic activity among the series,which are also much better than those of the pristine ultrafine Pt/C.Besides,it also has a greatly enhanced electrochemical stability.In addition,the effects of annealing temperature and time are further investigated.More importantly,such superior ORR electrocatalytic performance of L1_(2)-Pt_3Co_(0.7)Mn_(0.3)/~SPt INPs/C are also well demonstrated in practical fuel cells.Physicochemical characterization analyses further reveal the major origins of the greatly enhanced ORR electrocata lytic performance:the Pt-Co-Mn alloy-induced geometric and ligand effects as well as the extremely high L1_(2) atomic-ordering degree.This work not only successfully develops a highly active and stable ordered ternary intermetallic ORR electrocatalyst,but also elucidates the corresponding"structure-function"relationship,which can be further applied in designing other intermetallic(electro)catalysts.
基金supported by the National Natural Science Foundation of China (Nos. 21277008 and 20777005)National Key Research and Development Program of China (No. 2017YFC0209905)。
文摘The cryptomelane-type manganese oxide (OMS-2)-supported Co (x Co/OMS-2;x=5,10,and15 wt.%) catalysts were prepared via a pre-incorporation route.The as-prepared materials were used as catalysts for catalytic oxidation of toluene (2000 ppmV).Physical and chemical properties of the catalysts were measured using the X-ray diffraction (XRD),Fourier transform infrared spectroscopic (FT-IR),scanning electron microscopic (SEM),X-ray photoelectron spectroscopy (XPS),and hydrogen temperature-programmed reduction (H_(2)-TPR)techniques.Among all of the catalysts,10Co/OMS-2 performed the best,with the T90%,specific reaction rate at 245℃,and turnover frequency at 245℃ (TOFCo) being 245℃,1.23×10^(-3)moltoluene/(gcat·sec),and 11.58×10^(-3)sec-1for toluene oxidation at a space velocity of 60,000mL/(g·hr),respectively.The excellent catalytic performance of 10Co/OMS-2 were due to more oxygen vacancies,enhanced redox ability and oxygen mobility,and strong synergistic effect between Co species and OMS-2 support.Moreover,in the presence of poisoning gases CO_(2),SO_(2)or NH_(3),the activity of 10Co/OMS-2 decreased for the carbonate,sulfate and ammonia species covered the active sites and oxygen vacancies,respectively.After the activation treatment,the catalytic activity was partly recovered.The good low-temperature reducibility of 10Co/OMS-2 could also facilitate the redox process accompanied by the consecutive electron transfer between the adsorbed O_(2)and the cobalt or manganese ions.In the oxidation process of toluene,the benzoic and aldehydic intermediates werefirst generated,which were further oxidized to the benzoate intermediate that were eventually converted into H_(2)O and CO_(2).
