Lead(Pb)-zinc(Zn)slags contain large amounts of Pb,causing irreversible damage to the environment.Therefore,developing an effective strategy to extract Pb from Pb-Zn slags and convert them into a renewable high-value ...Lead(Pb)-zinc(Zn)slags contain large amounts of Pb,causing irreversible damage to the environment.Therefore,developing an effective strategy to extract Pb from Pb-Zn slags and convert them into a renewable high-value catalyst not only solves the energy crisis but also reduces environmental pollution.Herein,we present a viable strategy to recycle Pb and iron(Fe)from Pb-Zn slags for the fabrication of efficient methylammonium lead tri-iodide(r-MAPbI_(3))piezocatalysts with single-atom Fe-N_(4) sites.Intriguingly,atomically dispersed Fe sites from Pb-Zn slags,which coordinated with N in the neighboring four CH3NH3 to form the FeN_(4) configuration,were detected in the as-obtained r-MAPbI_(3) by synchrotron X-ray absorption spectroscopy.The introduction of Fe single atoms amplified the polarization of MAPbI_(3) and upshifted the d-band center of MAPbI_(3).This not only enhanced the piezoelectric response of MAPbI_(3) but also promoted the proton transfer during the hydrogen evolution process.Due to the decoration of Fe single atoms,r-MAPbI_(3) showed a pronounced H2 yield of 322.4μmol g^(−1) h^(−1),which was 2.52 times that of MAPbI_(3) synthesized using commercially available reagents.This simple yet robust strategy to manufactureMAPbI_(3) piezocatalysts paves a novel way to the large-scale and value-added consumption of Pb-containing waste residues.展开更多
Atomically dispersed metals stabilized by nitrogen elements in carbon skeleton hold great promise as alternatives for Pt-based catalysts towards oxygen reduction reaction in proton exchange membrane fuel cells.However...Atomically dispersed metals stabilized by nitrogen elements in carbon skeleton hold great promise as alternatives for Pt-based catalysts towards oxygen reduction reaction in proton exchange membrane fuel cells.However,their widespread commercial applications are limited by complicated synthetic procedures for mass production.Herein,we are proposing a simple,green mechanochemical approach to synthesize zeolitic imidazolate frameworks precursors for the production of atomically dispersed“Fe-N_(4)”sites in holey carbon nanosheets on a large scale.The thin porous carbon nanosheets(PCNs)with atomically dispersed“Fe-N_(4)”moieties can be prepared in hectogram scale by directly pyrolysis of salt-sealed Fe-based zeolitic imidazolate framework-8(Fe-ZIF-8@NaCl)precursors.The PCNs possess large specific surface area,abundant lamellar edges and rich“Fe-N_(4)”active sites,and show superior catalytic activity towards oxygen reduction reaction in an acid electrolyte.This work provides a promising approach to cost-effective production of atomically dispersed transition metal catalysts on large scale for practical applications.展开更多
Hydroxyl radical(·OH)formation from Fe(Ⅱ)-bearing clay mineral oxygenation in the shallow subsurface has been well documented under moderate environmental conditions.However,the impact of freezing processes on t...Hydroxyl radical(·OH)formation from Fe(Ⅱ)-bearing clay mineral oxygenation in the shallow subsurface has been well documented under moderate environmental conditions.However,the impact of freezing processes on the·OH production capability of Fe(Ⅱ)-bearing clay minerals for organic contaminant degradation,particularly in seasonally frozen soils,remains unclear.In this study,we investigated the influence of pre-freezing durations on the mineral proprieties,·OH production,and phenol degradation during the oxygenation of reduced Fe-rich nontronite(rNAu-2)and Fe-poor montmorillonite(rSWy-3).During the freezing process of reduced clay minerals(1 mM Fe(Ⅱ)),the content of edge surface Fe and Fe(Ⅱ)decreased by up to 46%and 58%,respectively,followed by a slight increased as clay mineral particles aggregated and subsequently partially disaggregated.As the edge surface Fe(Ⅱ)is effective in O_(2) activation but less effective in the transformation of H_(2)O_(2) to·OH,the redistribution of edge surface Fe(Ⅱ)leads to that·OH production and phenol degradation increased initially and then decreased with pre-freezing durations ranging from 0 to 20 days.Moreover,the rate constants of phenol degradation for both the rapid and slow reaction phases also first increase and then decrease with freezing time.However,pre-freezing significantly influenced the rapid phase of phenol degradation by rNAu-2 but affected the slow phase by rSWy-3 due to the much higher edge-surface Fe(Ⅱ)content in rNAu-2.Overall,these findings provide novel insights into the mechanism of·OH production and contaminant degradation during the freeze-thaw processes in clay-rich soils.展开更多
The process of γ(fcc)→γ(fcc)+γ'(L12)phase transformation was simulated by using microscopic phase-field method for the low supersaturation NiAl9Fe6 alloy.It is found that in the γ' phase,the ordering degr...The process of γ(fcc)→γ(fcc)+γ'(L12)phase transformation was simulated by using microscopic phase-field method for the low supersaturation NiAl9Fe6 alloy.It is found that in the γ' phase,the ordering degree of Al atoms is obviously higher than that of Fe atoms,and the ordering of Al atoms precedes their clustering,while the case of Fe atoms is opposite.The α site is mainly occupied by Ni atoms,while the β site is occupied in common by Al,Fe and Ni atoms.At order-disorder interphase boundary,the ordering degree of Al atoms is higher than that of Fe atoms,and at the β site,the Fe atomic site occupation probabilities vary from high to low during ordering;the Al atomic site occupation probabilities are similar to those of Fe atoms,but their values are much higher than those of Fe atoms;Ni atoms are opposite to both of them.Meanwhile,during the ordering transformation,γ' phase is always a complex Ni3(AlFeNi)single-phase,and it is precipitated by the non-classical nucleation and growth style.Finally,in the alloy system,the volume of γ' ordered phase is less than that of γ phase,and the volume ratio of order to disorder is about 77%.展开更多
基金supported by the Foundation for Innovative Research Groups of the National Natural Science Foundation of China(No.52121004,U23B20166)Guangdong Basic and Applied Basic Research Foundation(2024A1515030039,2025A1515010312).
文摘Lead(Pb)-zinc(Zn)slags contain large amounts of Pb,causing irreversible damage to the environment.Therefore,developing an effective strategy to extract Pb from Pb-Zn slags and convert them into a renewable high-value catalyst not only solves the energy crisis but also reduces environmental pollution.Herein,we present a viable strategy to recycle Pb and iron(Fe)from Pb-Zn slags for the fabrication of efficient methylammonium lead tri-iodide(r-MAPbI_(3))piezocatalysts with single-atom Fe-N_(4) sites.Intriguingly,atomically dispersed Fe sites from Pb-Zn slags,which coordinated with N in the neighboring four CH3NH3 to form the FeN_(4) configuration,were detected in the as-obtained r-MAPbI_(3) by synchrotron X-ray absorption spectroscopy.The introduction of Fe single atoms amplified the polarization of MAPbI_(3) and upshifted the d-band center of MAPbI_(3).This not only enhanced the piezoelectric response of MAPbI_(3) but also promoted the proton transfer during the hydrogen evolution process.Due to the decoration of Fe single atoms,r-MAPbI_(3) showed a pronounced H2 yield of 322.4μmol g^(−1) h^(−1),which was 2.52 times that of MAPbI_(3) synthesized using commercially available reagents.This simple yet robust strategy to manufactureMAPbI_(3) piezocatalysts paves a novel way to the large-scale and value-added consumption of Pb-containing waste residues.
基金the National Key Research and Development Program of China(No.2017YFA0206500)the Key Program of National Natural Science Foundation of China(No.51732002)+3 种基金National Natural Science Foundation of China(No.21971002)the Fundamental Research Funds for the Central Universities(Nos.buctrc202118 and buctrc202007)Distinguished Scientist Program at BUCT(No.buctylkxj02)Beijing Advanced Innovation Center for Soft Matter Science and Engineering.
文摘Atomically dispersed metals stabilized by nitrogen elements in carbon skeleton hold great promise as alternatives for Pt-based catalysts towards oxygen reduction reaction in proton exchange membrane fuel cells.However,their widespread commercial applications are limited by complicated synthetic procedures for mass production.Herein,we are proposing a simple,green mechanochemical approach to synthesize zeolitic imidazolate frameworks precursors for the production of atomically dispersed“Fe-N_(4)”sites in holey carbon nanosheets on a large scale.The thin porous carbon nanosheets(PCNs)with atomically dispersed“Fe-N_(4)”moieties can be prepared in hectogram scale by directly pyrolysis of salt-sealed Fe-based zeolitic imidazolate framework-8(Fe-ZIF-8@NaCl)precursors.The PCNs possess large specific surface area,abundant lamellar edges and rich“Fe-N_(4)”active sites,and show superior catalytic activity towards oxygen reduction reaction in an acid electrolyte.This work provides a promising approach to cost-effective production of atomically dispersed transition metal catalysts on large scale for practical applications.
基金supported by the National Natural Science Foundation of China(Nos.U22A20591,42077185,42107217)the Sichuan Province Science and Technology Program for Distinguished Young Scholars(No.2022JDJQ0010)+1 种基金the Sichuan Science and Technology Program(No.2024NSFSC0842)the State Key Laboratory of Geohazard Prevention and Geoenvironment Protection(No.SKLGP2020Z002)。
文摘Hydroxyl radical(·OH)formation from Fe(Ⅱ)-bearing clay mineral oxygenation in the shallow subsurface has been well documented under moderate environmental conditions.However,the impact of freezing processes on the·OH production capability of Fe(Ⅱ)-bearing clay minerals for organic contaminant degradation,particularly in seasonally frozen soils,remains unclear.In this study,we investigated the influence of pre-freezing durations on the mineral proprieties,·OH production,and phenol degradation during the oxygenation of reduced Fe-rich nontronite(rNAu-2)and Fe-poor montmorillonite(rSWy-3).During the freezing process of reduced clay minerals(1 mM Fe(Ⅱ)),the content of edge surface Fe and Fe(Ⅱ)decreased by up to 46%and 58%,respectively,followed by a slight increased as clay mineral particles aggregated and subsequently partially disaggregated.As the edge surface Fe(Ⅱ)is effective in O_(2) activation but less effective in the transformation of H_(2)O_(2) to·OH,the redistribution of edge surface Fe(Ⅱ)leads to that·OH production and phenol degradation increased initially and then decreased with pre-freezing durations ranging from 0 to 20 days.Moreover,the rate constants of phenol degradation for both the rapid and slow reaction phases also first increase and then decrease with freezing time.However,pre-freezing significantly influenced the rapid phase of phenol degradation by rNAu-2 but affected the slow phase by rSWy-3 due to the much higher edge-surface Fe(Ⅱ)content in rNAu-2.Overall,these findings provide novel insights into the mechanism of·OH production and contaminant degradation during the freeze-thaw processes in clay-rich soils.
基金Project(50671084)supported by the National Natural Science Foundation of ChinaProject(Z200714)supported by Graduate Starting Seed Fund of Northwestern Polythechnical University,China
文摘The process of γ(fcc)→γ(fcc)+γ'(L12)phase transformation was simulated by using microscopic phase-field method for the low supersaturation NiAl9Fe6 alloy.It is found that in the γ' phase,the ordering degree of Al atoms is obviously higher than that of Fe atoms,and the ordering of Al atoms precedes their clustering,while the case of Fe atoms is opposite.The α site is mainly occupied by Ni atoms,while the β site is occupied in common by Al,Fe and Ni atoms.At order-disorder interphase boundary,the ordering degree of Al atoms is higher than that of Fe atoms,and at the β site,the Fe atomic site occupation probabilities vary from high to low during ordering;the Al atomic site occupation probabilities are similar to those of Fe atoms,but their values are much higher than those of Fe atoms;Ni atoms are opposite to both of them.Meanwhile,during the ordering transformation,γ' phase is always a complex Ni3(AlFeNi)single-phase,and it is precipitated by the non-classical nucleation and growth style.Finally,in the alloy system,the volume of γ' ordered phase is less than that of γ phase,and the volume ratio of order to disorder is about 77%.
基金Project (51002128) supported by the National Natural Science Foundation of ChinaProject (2012M511737) supported by the National Science Foundation for Post-Doctor of China
文摘研制高活性的Fe/N/C氧还原催化剂对于降低燃料电池成本、实现商业化应用有重要意义.为实现Fe/N/C催化剂的理性设计,需要深入研究其活性位结构.本文发展一种研究活性位结构的新策略,以预先合成好的聚间苯二胺基Fe/N/C催化剂(Pm PDA-Fe Nx/C)为起始物,对其在1000~1500 o C高温下再次进行热处理并使其失活,通过关联催化剂热处理前后的结构变化与氧还原催化性能来揭示活性位结构.实验结果表明,随着热处理温度升高,活性中心结构被破坏,铁原子析出团聚并形成纳米颗粒,氮元素挥发损失,导致催化剂失活.XPS分析显示,低结合能含氮物种的含量与催化剂的ORR活性呈良好的正相关性,表明活性中心很可能是由吡啶N和Fe-N物种构成的.
