Na-rich birnessite（NRB） was synthesized by a simple synthesis method and used as a high-efficiency adsorbent for the removal of ammonium ion（NH＋4） from aqueous solution.In order to demonstrate the adsorption perf...Na-rich birnessite（NRB） was synthesized by a simple synthesis method and used as a high-efficiency adsorbent for the removal of ammonium ion（NH＋4） from aqueous solution.In order to demonstrate the adsorption performance of the synthesized material,the effects of contact time,pH,initial ammonium ion concentration,and temperature were investigated.Adsorption kinetics showed that the adsorption behavior followed the pseudo second-order kinetic model.The equilibrium adsorption data were fitted to Langmuir and Freundlich adsorption models and the model parameters were evaluated.The monolayer adsorption capacity of the adsorbent,as obtained from the Langmuir isotherm,was 22.61 mg NH＋4-N/g at283 K.Thermodynamic analyses showed that the adsorption was spontaneous and that it was also a physisorption process.Our data revealed that the higher NH＋4adsorption capacity could be primarily attributed to the water absorption process and electrostatic interaction.Particularly,the high surface hydroxyl-content of NRB enables strong interactions with ammonium ion.The results obtained in this study illustrate that the NRB is expected to be an effective and economically viable adsorbent for ammonium ion removal from aqueous system.展开更多
Birnessite is a common weathering and oxidation product of manganese-bearing rocks. An O2 oxidation procedure of Mn(OH)2 in the alkali medium has been used to synthesize birnessite. Fast and powder X-ray diffraction (...Birnessite is a common weathering and oxidation product of manganese-bearing rocks. An O2 oxidation procedure of Mn(OH)2 in the alkali medium has been used to synthesize birnessite. Fast and powder X-ray diffraction (XRD), transmission electron microscopy (TEM), electron diffraction (ED), energy dispersed X-ray analysis (EDAX), infrared spectroscopy (IR) techniques and chemical composition analysis, Eh-pH equilibrium diagram approaches were employed to investigate the reaction process and pathways of birnessite formation. Results showed that the process of the birnessite formation could be divided into four stages: (1) forma- tion stage for hausmannite and feitknechtite, (2) stage of transformation of hausmannite and feitknechtite to buserite, (3) buserite crystal growing stage, and (4) stage of conversion of buser- ite into birnessite. Mn(OH)2 was mainly present as amorphous state only for a short initial time of oxidation reaction. In the oxidation process, buserite formed following two pathways by recrys- tallization after dissolution of the intermediates, and the transformations of the minerals de- pended on the Eh determined by the dissolved O2 concentration on their surfaces. The results are fundamental in further exploration on the mechanism of birnessite formation in the alkali medium. A great practical significance would also be expected with respect to the areas of mate- rial sciences.展开更多
The characteristics of Pb^2＋ adsorption on the surface of birnessites with different average oxidation states （AOS） of Mn, synthesized under acidic and alkali conditions, were investigated. The results indicated th...The characteristics of Pb^2＋ adsorption on the surface of birnessites with different average oxidation states （AOS） of Mn, synthesized under acidic and alkali conditions, were investigated. The results indicated that the amount of adsorbed Pb^2＋ increased with the increase of Mn AOS in birnessites. The amount of Pb〉 adsorbed positively correlated with the amount of released Mn^2＋, H^＋, and K^＋ （r = 0.9962 〉 0.6614, n = 14, ct = 0.01）. The released Mn^2＋, H^＋, and K^＋ were derived mostly from the corresponding cations adsorbed on the vacant sites. The maximum amount of adsorbed Pb^2＋ increased with the increasing vacant cation sites, leading to an increase of the total amount of released Mn^2＋, H^＋, and K^＋, and the increased likelihood for two Pb^2＋ adsorbed in the region of one side of a vacant site.展开更多
Single phase and well-crystallined todorokite were synthesized by heating and refluxing process from birnessite as a precursor. The average chemical composition of the synthesized todorokites by refluxing for 8 h and ...Single phase and well-crystallined todorokite were synthesized by heating and refluxing process from birnessite as a precursor. The average chemical composition of the synthesized todorokites by refluxing for 8 h and for 24 h was Mg0.19MnO2.11(H2O)1.15 and in0.17-MnO2.10(H2O)0.88, respectively. The crystallinity of the todorokite increased and no other phase was produced with increasing refluxing period. The synthesized todorokites have the same morphologies and the similar structural characteristics with the natural todorokites and hydro-thermally synthesized samples. The chemical compositions of the synthetic tordorokites by refluxing process are close to those of todorokites synthesized by hydrothermal process, except a higher average oxidation state of Mn for the former.展开更多
Mn-based rechargeable aqueous zinc-ion batteries(ZIBs)are highly promising because of their high operating voltages,attractive energy densities,and eco-friendliness.However,the electrochemical performances of Mn-based...Mn-based rechargeable aqueous zinc-ion batteries(ZIBs)are highly promising because of their high operating voltages,attractive energy densities,and eco-friendliness.However,the electrochemical performances of Mn-based cathodes usually suffer from their serious structure transformation upon charge/discharge cycling.Herein,we report a layered sodium-ion/crystal water co-intercalated Birnessite cathode with the formula of Na0.55Mn2O4·0.57H2O(NMOH)for high-performance aqueous ZIBs.A displacement/intercalation electrochemical mechanism was confirmed in the Mn-based cathode for the first time.Na+and crystal water enlarge the interlayer distance to enhance the insertion of Zn^2+,and some sodium ions are replaced with Zn^2+ in the first cycle to further stabilize the layered structure for subsequent reversible Zn^2+/H^+ insertion/extraction,resulting in exceptional specific capacities and satisfactory structural stabilities.Additionally,a pseudo-capacitance derived from the surface-adsorbed Na^+ also contributes to the electrochemical performances.The NMOH cathode not only delivers high reversible capacities of 389.8 and 87.1 mA h g^−1 at current densities of 200 and 1500 mA g^−1,respectively,but also maintains a good long-cycling performance of 201.6 mA h g^−1 at a high current density of 500 mA g^−1 after 400 cycles,which makes the NMOH cathode competitive for practical applications.展开更多
Flaky and nanospherical birnessite and birnessite-supported Pt catalysts were successfully prepared and characterized by means of Xray diffraction （XRD）,transmission electron microscopy （TEM）,energy dispersive spe...Flaky and nanospherical birnessite and birnessite-supported Pt catalysts were successfully prepared and characterized by means of Xray diffraction （XRD）,transmission electron microscopy （TEM）,energy dispersive spectroscopy （EDS） and N2 adsorption-desorption.Effects of the birnessite morphology and Pt reduction method on the catalytic activity for the complete oxidation of formaldehyde （HCHO） were investigated.It was found that flaky birnessite exhibited higher catalytic activity than nanospherical birnessite.The promoting effect of Pt on the birnessite catalyst indicated that the reduction method of the Pt precursor greatly influenced the catalytic performance.Flaky birnessite-supported Pt nanoparticles reduced by KBH 4 showed the highest catalytic activity and could completely oxidize HCHO into CO2 and H2O at 50℃,whereas the sample reduced using H2-plasma showed lower activity for HCHO oxidation.The differences in catalytic activity of these materials were jointly attributed to the effects of pore structure,surface active sites exposed to HCHO and the dispersion of Pt nanoparticles.展开更多
Birnessite is ubiquitous in the natural environment where heavy metals are retained and easily transformed.The surface properties and structure of birnessite change with the changes in external environmental condition...Birnessite is ubiquitous in the natural environment where heavy metals are retained and easily transformed.The surface properties and structure of birnessite change with the changes in external environmental conditions,which also affects the fate of heavy metals.Clarifying the effect and mechanism of the birnessite phase transition process on heavy metals is the key to taking effective measures to prevent and control heavy metal pollution.Therefore,the four transformation pathways of birnessite are summarized first in this review.Second,the relationship between transformation pathways and environmental conditions is proposed.These relevant environmental conditions include abiotic(e.g.,co-existing ions,pH,oxygen pressure,temperature,electric field,light,aging,pressure)and biotic factors(e.g.,microorganisms,biomolecules).The phase transformation is achieved by the key intermediate of Mn(Ⅲ)through interlayer-condensation,folding,neutralizationdisproportionation,and dissolution-recrystallization mechanisms.The AOS(average oxidation state)of Mn and interlayer spacing are closely correlated with the phase transformation of birnessite.Last but not least,the mechanisms of heavy metals immobilization in the transformation process of birnessite are summed up.They involve isomorphous substitution,redox,complexation,hydration/dehydration,etc.The transformation of birnessite and its implication on heavy metals will be helpful for understanding and predicting the behavior of heavy metals and the crucial phase of manganese oxides/hydroxides in natural and engineered environments.展开更多
The layeredδ-MnO_(2)(dMO)is an excellent cathode material for rechargeable aqueous zinc-ion batteries owing to its large interlayer distance(~0.7 nm),high capacity,and low cost;however,such cathodes suffer from struc...The layeredδ-MnO_(2)(dMO)is an excellent cathode material for rechargeable aqueous zinc-ion batteries owing to its large interlayer distance(~0.7 nm),high capacity,and low cost;however,such cathodes suffer from structural degradation during the long-term cycling process,leading to capacity fading.In this study,a Co-doped dMO composite with reduced graphene oxide(GC-dMO)is developed using a simple cost-effective hydrothermal method.The degree of disorderness increases owing to the hetero-atom doping and graphene oxide composites.It is demonstrated that layered dMO and GC-dMO undergo a structural transition from K-birnessite to the Zn-buserite phase upon the first discharge,which enhances the intercalation of Zn^(2+)ions,H_(2)O molecules in the layered structure.The GC-dMO cathode exhibits an excellent capacity of 302 mAh g^(-1)at a current density of 100 mAg^(-1)after 100 cycles as compared with the dMO cathode(159 mAhg^(-1)).The excellent electrochemical performance of the GC-dMO cathode owing to Co-doping and graphene oxide sheets enhances the interlayer gap and disorderness,and maintains structural stability,which facilitates the easy reverse intercalation and de-intercalation of Zn^(2+)ions and H_(2)O molecules.Therefore,GC-dMO is a promising cathode material for large-scale aqueous ZIBs.展开更多
基金supported by the National Natural Science Foundation of China(No.51278409)the Education Department of Shaanxi Province(No.15JS046)
文摘Na-rich birnessite（NRB） was synthesized by a simple synthesis method and used as a high-efficiency adsorbent for the removal of ammonium ion（NH＋4） from aqueous solution.In order to demonstrate the adsorption performance of the synthesized material,the effects of contact time,pH,initial ammonium ion concentration,and temperature were investigated.Adsorption kinetics showed that the adsorption behavior followed the pseudo second-order kinetic model.The equilibrium adsorption data were fitted to Langmuir and Freundlich adsorption models and the model parameters were evaluated.The monolayer adsorption capacity of the adsorbent,as obtained from the Langmuir isotherm,was 22.61 mg NH＋4-N/g at283 K.Thermodynamic analyses showed that the adsorption was spontaneous and that it was also a physisorption process.Our data revealed that the higher NH＋4adsorption capacity could be primarily attributed to the water absorption process and electrostatic interaction.Particularly,the high surface hydroxyl-content of NRB enables strong interactions with ammonium ion.The results obtained in this study illustrate that the NRB is expected to be an effective and economically viable adsorbent for ammonium ion removal from aqueous system.
基金supported by the National Natural Science Foundation of China(Grant Nos.40403009 and 40101017)by Research Fund for the Doctoral Program of Higher Education(Grant No.2002050411).
文摘Birnessite is a common weathering and oxidation product of manganese-bearing rocks. An O2 oxidation procedure of Mn(OH)2 in the alkali medium has been used to synthesize birnessite. Fast and powder X-ray diffraction (XRD), transmission electron microscopy (TEM), electron diffraction (ED), energy dispersed X-ray analysis (EDAX), infrared spectroscopy (IR) techniques and chemical composition analysis, Eh-pH equilibrium diagram approaches were employed to investigate the reaction process and pathways of birnessite formation. Results showed that the process of the birnessite formation could be divided into four stages: (1) forma- tion stage for hausmannite and feitknechtite, (2) stage of transformation of hausmannite and feitknechtite to buserite, (3) buserite crystal growing stage, and (4) stage of conversion of buser- ite into birnessite. Mn(OH)2 was mainly present as amorphous state only for a short initial time of oxidation reaction. In the oxidation process, buserite formed following two pathways by recrys- tallization after dissolution of the intermediates, and the transformations of the minerals de- pended on the Eh determined by the dissolved O2 concentration on their surfaces. The results are fundamental in further exploration on the mechanism of birnessite formation in the alkali medium. A great practical significance would also be expected with respect to the areas of mate- rial sciences.
基金supported by the National Natural Science Foundation of China (No. 40471070)the National Excellent Doctoral Dissertation of China(No. 200767)
文摘The characteristics of Pb^2＋ adsorption on the surface of birnessites with different average oxidation states （AOS） of Mn, synthesized under acidic and alkali conditions, were investigated. The results indicated that the amount of adsorbed Pb^2＋ increased with the increase of Mn AOS in birnessites. The amount of Pb〉 adsorbed positively correlated with the amount of released Mn^2＋, H^＋, and K^＋ （r = 0.9962 〉 0.6614, n = 14, ct = 0.01）. The released Mn^2＋, H^＋, and K^＋ were derived mostly from the corresponding cations adsorbed on the vacant sites. The maximum amount of adsorbed Pb^2＋ increased with the increasing vacant cation sites, leading to an increase of the total amount of released Mn^2＋, H^＋, and K^＋, and the increased likelihood for two Pb^2＋ adsorbed in the region of one side of a vacant site.
基金This work was supported by the National Natural Science Foundation of China(Grant Nos.40101017 and 40071048) by the Research Fund for the Doctoral Program of Higher Education(Grant No.2002050411).
文摘Single phase and well-crystallined todorokite were synthesized by heating and refluxing process from birnessite as a precursor. The average chemical composition of the synthesized todorokites by refluxing for 8 h and for 24 h was Mg0.19MnO2.11(H2O)1.15 and in0.17-MnO2.10(H2O)0.88, respectively. The crystallinity of the todorokite increased and no other phase was produced with increasing refluxing period. The synthesized todorokites have the same morphologies and the similar structural characteristics with the natural todorokites and hydro-thermally synthesized samples. The chemical compositions of the synthetic tordorokites by refluxing process are close to those of todorokites synthesized by hydrothermal process, except a higher average oxidation state of Mn for the former.
基金Financial support from the National Natural Science Foundation of China (51972016, 51533001)the National Key Research and Development Program of China (2016YFC0801302)State Key Laboratory of Organic-Inorganic Composites (oic-201801002)
文摘Mn-based rechargeable aqueous zinc-ion batteries(ZIBs)are highly promising because of their high operating voltages,attractive energy densities,and eco-friendliness.However,the electrochemical performances of Mn-based cathodes usually suffer from their serious structure transformation upon charge/discharge cycling.Herein,we report a layered sodium-ion/crystal water co-intercalated Birnessite cathode with the formula of Na0.55Mn2O4·0.57H2O(NMOH)for high-performance aqueous ZIBs.A displacement/intercalation electrochemical mechanism was confirmed in the Mn-based cathode for the first time.Na+and crystal water enlarge the interlayer distance to enhance the insertion of Zn^2+,and some sodium ions are replaced with Zn^2+ in the first cycle to further stabilize the layered structure for subsequent reversible Zn^2+/H^+ insertion/extraction,resulting in exceptional specific capacities and satisfactory structural stabilities.Additionally,a pseudo-capacitance derived from the surface-adsorbed Na^+ also contributes to the electrochemical performances.The NMOH cathode not only delivers high reversible capacities of 389.8 and 87.1 mA h g^−1 at current densities of 200 and 1500 mA g^−1,respectively,but also maintains a good long-cycling performance of 201.6 mA h g^−1 at a high current density of 500 mA g^−1 after 400 cycles,which makes the NMOH cathode competitive for practical applications.
基金supported by the National Natural Science Foundation of China (No. 20871118,21007076)the Knowledge Innovation Program of the Chinese Academy of Sciences (CAS) (No. KSCX2-YW-G-059)+1 种基金the National Basic Research Program (973) of China (No.2010CB934103)the "Hundred Talents Program" of CAS
文摘Flaky and nanospherical birnessite and birnessite-supported Pt catalysts were successfully prepared and characterized by means of Xray diffraction （XRD）,transmission electron microscopy （TEM）,energy dispersive spectroscopy （EDS） and N2 adsorption-desorption.Effects of the birnessite morphology and Pt reduction method on the catalytic activity for the complete oxidation of formaldehyde （HCHO） were investigated.It was found that flaky birnessite exhibited higher catalytic activity than nanospherical birnessite.The promoting effect of Pt on the birnessite catalyst indicated that the reduction method of the Pt precursor greatly influenced the catalytic performance.Flaky birnessite-supported Pt nanoparticles reduced by KBH 4 showed the highest catalytic activity and could completely oxidize HCHO into CO2 and H2O at 50℃,whereas the sample reduced using H2-plasma showed lower activity for HCHO oxidation.The differences in catalytic activity of these materials were jointly attributed to the effects of pore structure,surface active sites exposed to HCHO and the dispersion of Pt nanoparticles.
基金supported by the National Natural Science Foundation of China(Nos.51974379,52274414)the Foundation for Innovative Research Groups of the National Natural Science Foundation of China(No.52121004)+2 种基金the Project of National Science Fund for Excellent Young Scholars of China(No.52022111)the National Key R&D Program of China(No.2022YFD1700101)the Huxiang Youth Talent Support Program(No.2020RC3012)。
文摘Birnessite is ubiquitous in the natural environment where heavy metals are retained and easily transformed.The surface properties and structure of birnessite change with the changes in external environmental conditions,which also affects the fate of heavy metals.Clarifying the effect and mechanism of the birnessite phase transition process on heavy metals is the key to taking effective measures to prevent and control heavy metal pollution.Therefore,the four transformation pathways of birnessite are summarized first in this review.Second,the relationship between transformation pathways and environmental conditions is proposed.These relevant environmental conditions include abiotic(e.g.,co-existing ions,pH,oxygen pressure,temperature,electric field,light,aging,pressure)and biotic factors(e.g.,microorganisms,biomolecules).The phase transformation is achieved by the key intermediate of Mn(Ⅲ)through interlayer-condensation,folding,neutralizationdisproportionation,and dissolution-recrystallization mechanisms.The AOS(average oxidation state)of Mn and interlayer spacing are closely correlated with the phase transformation of birnessite.Last but not least,the mechanisms of heavy metals immobilization in the transformation process of birnessite are summed up.They involve isomorphous substitution,redox,complexation,hydration/dehydration,etc.The transformation of birnessite and its implication on heavy metals will be helpful for understanding and predicting the behavior of heavy metals and the crucial phase of manganese oxides/hydroxides in natural and engineered environments.
基金supported by the National Research Foundation of Korea(NRF)grants funded by the Korean Government(NRF-2021R1A4A1030318,NRF-2022R1C1C1011386,NRF-2020M3H4A1A03084258)supported by the"Regional Innovation Strategy(RIS)"through the National Research Foundation of Korea(NRF)funded by the Ministry of Education(MOE)(2021RIS-003)
文摘The layeredδ-MnO_(2)(dMO)is an excellent cathode material for rechargeable aqueous zinc-ion batteries owing to its large interlayer distance(~0.7 nm),high capacity,and low cost;however,such cathodes suffer from structural degradation during the long-term cycling process,leading to capacity fading.In this study,a Co-doped dMO composite with reduced graphene oxide(GC-dMO)is developed using a simple cost-effective hydrothermal method.The degree of disorderness increases owing to the hetero-atom doping and graphene oxide composites.It is demonstrated that layered dMO and GC-dMO undergo a structural transition from K-birnessite to the Zn-buserite phase upon the first discharge,which enhances the intercalation of Zn^(2+)ions,H_(2)O molecules in the layered structure.The GC-dMO cathode exhibits an excellent capacity of 302 mAh g^(-1)at a current density of 100 mAg^(-1)after 100 cycles as compared with the dMO cathode(159 mAhg^(-1)).The excellent electrochemical performance of the GC-dMO cathode owing to Co-doping and graphene oxide sheets enhances the interlayer gap and disorderness,and maintains structural stability,which facilitates the easy reverse intercalation and de-intercalation of Zn^(2+)ions and H_(2)O molecules.Therefore,GC-dMO is a promising cathode material for large-scale aqueous ZIBs.
