The problem of water and sulfur poisoning in flue gas atmosphere remains a significant obstacle for low-temperature deNO_(x) catalysts.This study investigated the sulfation mechanism of the CoMn_(2)O_(4)/CeTiO_(x)(CMC...The problem of water and sulfur poisoning in flue gas atmosphere remains a significant obstacle for low-temperature deNO_(x) catalysts.This study investigated the sulfation mechanism of the CoMn_(2)O_(4)/CeTiO_(x)(CMCT)catalyst during the selective catalytic reduction of NO_(x) with NH3 under conditions containing H2O and SO_(2) at 150℃.Employing a comprehensive suite of time-resolved analysis and characterization techniques,the evolution of sulfate species was systematically categorized into three stages:initial rapid surface sulfate accumulation,the transformation of surface sulfates to bulk metal sulfates,and partial sulfates decomposition after the removal of H2O and SO_(2).These findings indicate that bulk metal sulfates irreversibly deactivate the catalyst by distorting active component lattices and consuming oxygen vacancies,whereas surface sulfates(including ammonium sulfates and surface-coordinated metal sulfates)cause reversible performance loss through decomposition.Furthermore,the competitive adsorption of H2O and SO_(2) significantly influences the catalytic efficiency,with H2O suppressing SO_(2) adsorption while simultaneously enhancing the formation of Brönsted acid sites.This research underscores the critical role of sulfate dynamics on catalyst performance,revealing the enhanced SO_(2) resistance of the Eley-Rideal mechanism facilitated by the Ce-Ti support relative to the Langmuir-Hinshelwood pathway.Collectively,the study unravels the complex interplay of sulfate dynamics influencing catalyst performance and provides potential approaches to mitigate deactivation in demanding atmospheric conditions.展开更多
Regulating the orbital spin-electron filling of metal centers via interatomic electron transfer in transition metal oxides is one promising approach to enhancing their electrocatalytic oxygen evolution reaction(OER)pe...Regulating the orbital spin-electron filling of metal centers via interatomic electron transfer in transition metal oxides is one promising approach to enhancing their electrocatalytic oxygen evolution reaction(OER)performances,while it is still a challenge due to lacking of efficient strategy and deep understanding.In this work,a facile strategy containing electrochemical deposition and annealing in air atmosphere has been proposed to introduce monodispersed neodymium(Nd)atoms into spinel Co_(3)O_(4)nanosheets to trigger the electron transfer.Accordingly,the as-prepared Nd doped Co_(3)O_(4)nanosheets(Nd/Co_(3)O_(4))on nickel foam or carbon cloth showed greatly enhanced OER performances,with low overpotential of 284 and 396 mV at 10 m A cm^(-2),small Tafel slope of 95 and 119 mV dec^(-1)in 1.0 M KOH and 0.5 M H_(2)SO_(4),respectively.The experimental and density function theory results coherently indicate that the charge transfer in the Nd-O-Co asymmetric configuration not only enhances the conductivity of Co_(3)O_(4),but also regulates the filling degree of egorbitals of Co,leading to higher spin states,optimized adsorption ability,and accelerated H_(2)O dissociation process,thus achieving boosted OER activity.展开更多
Here we report that the presence of MgCO_(3) stimulates the extracellular polymeric substance (EPS) secretion of Microcystis Aeruginosa (M. Aeruginosa). This stimulation led to a significant reduction in the total con...Here we report that the presence of MgCO_(3) stimulates the extracellular polymeric substance (EPS) secretion of Microcystis Aeruginosa (M. Aeruginosa). This stimulation led to a significant reduction in the total concentration of NH_(4)^(+)‒N by more than 86%, and effective recovery of PO_(4)^(3-)‒P within three days from concentrated wastewater (WW), although the secreted EPS inhibited the conversion of MgCO_(3) to specific crystal forms (MgNH4PO4.6H2O or MgHPO4.7H2O). Moreover, with an increase in PO_(4)^(3-) concentration in WW, these crystals appeared, thus the removal of NH_(4)^(+)‒N and PO_(4)^(3-)‒P nutrients can be attributed to the combined effect of M. Aeruginosa and MgCO_(3). We used Surface-Enhanced Raman Spectroscopy (SERS) combined with X-ray Diffraction (XRD), Field Emission Scanning Electron Microscopy with Energy-Dispersive X-ray Spectroscopy (FESEM-EDS), and X-ray Photoelectron Spectroscopy (XPS) to investigate the mechanism for competitive interactions between M. Aeruginosa and MgCO_(3) in removing NH_(4)^(+)‒N and PO_(4)^(3-)‒P. We identified that the bound EPS accumulated amorphous Mg–P–O dense particles on M. Aeruginosa, while soluble EPS, containing –COOH groups of humic-like substances decreased the pH of the solution and coordinated with Mg^(2+) ions. Therefore, both secreted bound and soluble EPS play a vital role in hindering the transformation of Mg^(2+) ions or MgCO_(3) to MgNH4PO4.6H2O or MgHPO4.7H2O crystals within WW, and they enhanced M. Aeruginosa 's ability in absorbing nutrients of NH_(4)^(+)‒N and PO_(4)^(3-)‒P. This mechanism plays a crucial role in the efficient recovery of NH_(4)^(+)‒N and PO_(4)^(3-)‒P from concentrated wastewater sources such as aerobically or anaerobically digested effluent from various sources like agriculture, livestock, and domestic wastewaters.展开更多
Herein,a bottom-down design is presented to successfully fabricate ZIF-derived Co3O4,grown in situ on a one-dimensional(1D)α-MnO2 material,denoted as α-MnO2@Co3O4.The synergistic effect derived from the coupled inte...Herein,a bottom-down design is presented to successfully fabricate ZIF-derived Co3O4,grown in situ on a one-dimensional(1D)α-MnO2 material,denoted as α-MnO2@Co3O4.The synergistic effect derived from the coupled interface constructed betweenα-MnO2 and Co3O4 is responsible for the enhanced catalytic activity.The resultantα-MnO2@Co3O4 catalyst exhibits excellent catalytic activity at a T90%(temperature required to achieve a toluene conversion of 90%)of approximately 229℃,which is 47 and 28℃ lower than those of the pureα-MnO2 nanowire and Co3O4-b obtained via pyrolysis of ZIF-67,respectively.This activity is attributed to the increase in the number of surface-adsorbed oxygen species,which accelerate the oxygen mobility and enhance the redox pairs of Mn^4+/Mn^3+ and Co^2+/Co^3+.Moreover,the result of in situ diffuse reflectance infrared Fourier transform spectroscopy suggests that the gaseous oxygen could be more easily activated to adsorbed oxygen species on the surface of α-MnO2@Co3O4 than on that of α-MnO2.The catalytic reaction route of toluene oxidation over theα-MnO2@Co3O4 catalyst is as follows:toluene→benzoate species→alkanes containing oxygen functional group→CO2 and H2O.In addition,the α-MnO2@Co3O4 catalyst shows excellent stability and good water resistance for toluene oxidation.Furthermore,the preparation method can be extended to other 1D MnO2 materials.A new strategy for the development of high-performance catalysts of practical significance is provided.展开更多
文摘The problem of water and sulfur poisoning in flue gas atmosphere remains a significant obstacle for low-temperature deNO_(x) catalysts.This study investigated the sulfation mechanism of the CoMn_(2)O_(4)/CeTiO_(x)(CMCT)catalyst during the selective catalytic reduction of NO_(x) with NH3 under conditions containing H2O and SO_(2) at 150℃.Employing a comprehensive suite of time-resolved analysis and characterization techniques,the evolution of sulfate species was systematically categorized into three stages:initial rapid surface sulfate accumulation,the transformation of surface sulfates to bulk metal sulfates,and partial sulfates decomposition after the removal of H2O and SO_(2).These findings indicate that bulk metal sulfates irreversibly deactivate the catalyst by distorting active component lattices and consuming oxygen vacancies,whereas surface sulfates(including ammonium sulfates and surface-coordinated metal sulfates)cause reversible performance loss through decomposition.Furthermore,the competitive adsorption of H2O and SO_(2) significantly influences the catalytic efficiency,with H2O suppressing SO_(2) adsorption while simultaneously enhancing the formation of Brönsted acid sites.This research underscores the critical role of sulfate dynamics on catalyst performance,revealing the enhanced SO_(2) resistance of the Eley-Rideal mechanism facilitated by the Ce-Ti support relative to the Langmuir-Hinshelwood pathway.Collectively,the study unravels the complex interplay of sulfate dynamics influencing catalyst performance and provides potential approaches to mitigate deactivation in demanding atmospheric conditions.
基金support from the Natural Science Foundation and Overseas Talent Projects of Jiangxi Province(20242BAB25217,20232BAB214025,20232BCJ25044)the Jiangxi Provincial Natural Science Foundation(20232BAB204088)the National Natural Science Foundation of China(52402132)。
文摘Regulating the orbital spin-electron filling of metal centers via interatomic electron transfer in transition metal oxides is one promising approach to enhancing their electrocatalytic oxygen evolution reaction(OER)performances,while it is still a challenge due to lacking of efficient strategy and deep understanding.In this work,a facile strategy containing electrochemical deposition and annealing in air atmosphere has been proposed to introduce monodispersed neodymium(Nd)atoms into spinel Co_(3)O_(4)nanosheets to trigger the electron transfer.Accordingly,the as-prepared Nd doped Co_(3)O_(4)nanosheets(Nd/Co_(3)O_(4))on nickel foam or carbon cloth showed greatly enhanced OER performances,with low overpotential of 284 and 396 mV at 10 m A cm^(-2),small Tafel slope of 95 and 119 mV dec^(-1)in 1.0 M KOH and 0.5 M H_(2)SO_(4),respectively.The experimental and density function theory results coherently indicate that the charge transfer in the Nd-O-Co asymmetric configuration not only enhances the conductivity of Co_(3)O_(4),but also regulates the filling degree of egorbitals of Co,leading to higher spin states,optimized adsorption ability,and accelerated H_(2)O dissociation process,thus achieving boosted OER activity.
基金supported by Cultivating Fund Project of Hubei Hongshan Laboratory(2022hspy002).
文摘Here we report that the presence of MgCO_(3) stimulates the extracellular polymeric substance (EPS) secretion of Microcystis Aeruginosa (M. Aeruginosa). This stimulation led to a significant reduction in the total concentration of NH_(4)^(+)‒N by more than 86%, and effective recovery of PO_(4)^(3-)‒P within three days from concentrated wastewater (WW), although the secreted EPS inhibited the conversion of MgCO_(3) to specific crystal forms (MgNH4PO4.6H2O or MgHPO4.7H2O). Moreover, with an increase in PO_(4)^(3-) concentration in WW, these crystals appeared, thus the removal of NH_(4)^(+)‒N and PO_(4)^(3-)‒P nutrients can be attributed to the combined effect of M. Aeruginosa and MgCO_(3). We used Surface-Enhanced Raman Spectroscopy (SERS) combined with X-ray Diffraction (XRD), Field Emission Scanning Electron Microscopy with Energy-Dispersive X-ray Spectroscopy (FESEM-EDS), and X-ray Photoelectron Spectroscopy (XPS) to investigate the mechanism for competitive interactions between M. Aeruginosa and MgCO_(3) in removing NH_(4)^(+)‒N and PO_(4)^(3-)‒P. We identified that the bound EPS accumulated amorphous Mg–P–O dense particles on M. Aeruginosa, while soluble EPS, containing –COOH groups of humic-like substances decreased the pH of the solution and coordinated with Mg^(2+) ions. Therefore, both secreted bound and soluble EPS play a vital role in hindering the transformation of Mg^(2+) ions or MgCO_(3) to MgNH4PO4.6H2O or MgHPO4.7H2O crystals within WW, and they enhanced M. Aeruginosa 's ability in absorbing nutrients of NH_(4)^(+)‒N and PO_(4)^(3-)‒P. This mechanism plays a crucial role in the efficient recovery of NH_(4)^(+)‒N and PO_(4)^(3-)‒P from concentrated wastewater sources such as aerobically or anaerobically digested effluent from various sources like agriculture, livestock, and domestic wastewaters.
文摘Herein,a bottom-down design is presented to successfully fabricate ZIF-derived Co3O4,grown in situ on a one-dimensional(1D)α-MnO2 material,denoted as α-MnO2@Co3O4.The synergistic effect derived from the coupled interface constructed betweenα-MnO2 and Co3O4 is responsible for the enhanced catalytic activity.The resultantα-MnO2@Co3O4 catalyst exhibits excellent catalytic activity at a T90%(temperature required to achieve a toluene conversion of 90%)of approximately 229℃,which is 47 and 28℃ lower than those of the pureα-MnO2 nanowire and Co3O4-b obtained via pyrolysis of ZIF-67,respectively.This activity is attributed to the increase in the number of surface-adsorbed oxygen species,which accelerate the oxygen mobility and enhance the redox pairs of Mn^4+/Mn^3+ and Co^2+/Co^3+.Moreover,the result of in situ diffuse reflectance infrared Fourier transform spectroscopy suggests that the gaseous oxygen could be more easily activated to adsorbed oxygen species on the surface of α-MnO2@Co3O4 than on that of α-MnO2.The catalytic reaction route of toluene oxidation over theα-MnO2@Co3O4 catalyst is as follows:toluene→benzoate species→alkanes containing oxygen functional group→CO2 and H2O.In addition,the α-MnO2@Co3O4 catalyst shows excellent stability and good water resistance for toluene oxidation.Furthermore,the preparation method can be extended to other 1D MnO2 materials.A new strategy for the development of high-performance catalysts of practical significance is provided.
