Most studies have shown that oxygen vacancies on Ce_(x)Zr_(1-x)O_(2) solid solution are important for enhancing the catalytic oxidation performance.However,a handful of studies investigated the different roles of surf...Most studies have shown that oxygen vacancies on Ce_(x)Zr_(1-x)O_(2) solid solution are important for enhancing the catalytic oxidation performance.However,a handful of studies investigated the different roles of surface and subsurface oxygen vacancies on the performance and mechanisms of catalysts.Herein,a series of zirconium doping on CeO_(2) samples(CeO_(2),Ce_(0.95)Zr_(0.05)O_(2),and Ce_(0.8)5Zr_(0.15)O_(2))with various surface-to-subsurface oxygen vacancies ratios have been synthesized and applied in toluene catalytic oxidation.The obtained Ce_(0.95)Zr_(0.05)O_(2) exhibits an excellent catalytic performance with a 90%toluene conversion at 295℃,which is 68℃lower than that of CeO_(2).Additionally,the obtained Ce_(0.95)Zr_(0.05)O_(2)catalyst also exhibited good catalytic stability and water resistance.The XRD and HRTEM results show that Zr ions are incorporated into CeO_(2) lattice,forming Ce_(x)Zr_(1-x)O_(2) solid solution.Temperature-programmed experiments reveal that Ce_(0.95)Zr_(0.05)O_(2) shows excellent lowtemperature reducibility and abundant surface oxygen species.In-situ DRIFTS tests were used to probe the reaction mechanism,and the function of Zr doping in promoting the activation of oxygen was further determined.Density functional theory(DFT)calculations indicate that the vacancy formation energy and O_(2) adsorption energy are both lower on Ce_(0.95)Zr_(0.05)O_(2),confirming the reason for its superior catalytic performance.展开更多
Formaldehyde(HCHO)is a common indoor pollutant that is detrimental to human health.Its efficient removal has become an urgent demand to reduce the public health risk.In this work,Ag-MnO_(x)-based catalysts were prepar...Formaldehyde(HCHO)is a common indoor pollutant that is detrimental to human health.Its efficient removal has become an urgent demand to reduce the public health risk.In this work,Ag-MnO_(x)-based catalysts were prepared and activated under different atmosphere(i.e.,air,hydrogen(H_(2))and carbon monoxide(CO))for efficient oxidation of HCHO.The catalyst activated with CO(Ag/Mn-CO)displayed the highest activity among the tested samples with 90% conversion at 100℃ under a gas space velocity of 75,000 mL/(g_(cat)·hr).Complementary characterizations demonstrate that CO reduction treatment resulted in synergically regulated content of surface oxygen on support to adsorb/activate HCHO and size of Ag particle to dissociate oxygen to oxidize the adsorbed HCHO.In contrast,other catalysts lack for either abundant surface oxygen species or metallic silver with the appropriate particle size,so that the integrate activity is limited by one specific reaction step.This study contributes to elucidating the mechanisms regulating the oxidation activity of Ag-based catalysts.展开更多
Herein,a series of manganese oxide catalysts with different valences(Mn_(3)O_(4),Mn_(2)O_(3),and MnO_(2))were designed and synthesized for the synthesis of ethylene urea(EU)from ethylenediamine(EDA)and carbon dioxide(...Herein,a series of manganese oxide catalysts with different valences(Mn_(3)O_(4),Mn_(2)O_(3),and MnO_(2))were designed and synthesized for the synthesis of ethylene urea(EU)from ethylenediamine(EDA)and carbon dioxide(CO_(2)).With a maximal EDA conversion of 82%and EU selectivity of 99%at 160℃ for 2 h,Mn_(2)O_(3) catalysts had the best catalytic activity among them,which was superior to the reported catalysts.In the following order:Mn_(2)O_(3)>MnO_(2)>Mn_(3)O_(4),the catalytic activity for the synthesis of EU from CO_(2) and EDA decreased.Further characterization showed the Mn_(2)O_(3) catalyst possessed a greater Mn^(3+)/Mn4+ratio and more surface oxygen vacancies than the MnO_(2) and Mn_(3)O_(4),which improved its capacity to adsorb and activate CO_(2) and EDA.After four recycling runs,the EDA conversion slightly declined from 82%to 56%on Mn_(2)O_(3) catalyst,while no obvious change in EU selectivity was observed.The loss of surface Ov contents and Mn^(3+)proportion were concluded as main reasons for the decrease in catalytic activity over Mn_(2)O_(3) catalyst.This work demonstrated a metal oxide catalyst that was efficient in producing EU from CO_(2) and EDA.展开更多
To develop efficient catalysts for ambient carbon monoxide(CO)oxidation is significant for indoor air purification and also for many industrial applications.In this work,the catalytic activity for CO oxidation were en...To develop efficient catalysts for ambient carbon monoxide(CO)oxidation is significant for indoor air purification and also for many industrial applications.In this work,the catalytic activity for CO oxidation were enhanced by tuning the metal-support interaction of Ru/CeO_(2)catalysts.A series of Ru/CeO_(2)catalysts were synthesized by an impregnation method with calcination at 100,200,400 and 600℃,respectively,to regulate the Ru-CeO_(2)interaction.We discovered that low temperature calcination(100℃)induced more Ru-O-Ce bonds and stronger Ru-CeO_(2)interaction,while high temperature calcination(≥400℃)caused the agglomeration of Ru species with more Ru-O-Ru bonds and weaker Ru-CeO_(2)interaction,resulting in the lower redox capacity of these catalysts,as well as lower catalytic activity for CO oxidation.Only calcination at moderate 200℃ can induce the moderate interaction between Ru species and CeO_(2)support,which can keep the high dispersion of RuO_(x)species with the high redox capacity,thus leading to complete elimination of 500 ppm CO at room temperature on Ru/Ce-200 catalyst.展开更多
Co3O4/SiO2 catalysts for CO oxidation were prepared by conventional incipient wetness impregnation followed by calcination at various temperatures. Their structures were char- acterized with X-ray diffraction （XRD）,...Co3O4/SiO2 catalysts for CO oxidation were prepared by conventional incipient wetness impregnation followed by calcination at various temperatures. Their structures were char- acterized with X-ray diffraction （XRD）, laser Raman spectroscopy, X-ray photoelectron spectroscopy （XPS）, temperature-programmed reduction （TPR） and X-ray absorption fine structure （XAFS） spectroscopy. Both XRD and Raman spectroscopy only detect the existence of Co3O4 crystallites in all catalysts. However, XPS results indicate that excess Co2＋ ions are present on the surface of Co3O4 in Co3O4（200）/Si02 as compared with bulk Co3O4. Meanwhile, TPR results suggest the presence of surface oxygen vacancies on Co3O4 in Co3O4（200）/SiO2, and XAFS results demonstrate that Co3O4 in Co3O4（200）/SIO2 contains excess Co2＋. Increasing calcination temperature results in oxidation of excess Co2＋ and the decrease of the concentration of surface oxygen vacancies, consequently the for- mation of stoichiometric Co3O4 on supported catalysts. Among all Co3O4/SiO2 catalysts, Co3O4（200）/SiO2 exhibits the best catalytic performance towards CO oxidation, demonstrating that excess Co2＋ and surface oxygen vacancies can enhance the catalytic activity of Co3O4 towards CO oxidation. These results nicely demonstrate the effect of calcination temperature on the structure and catalytic performance towards CO oxidation of silicasupported Co3O4 catalysts and highlight the important role of surface oxygen vacancies on Co3O4.展开更多
Perovskite-type complex oxides ABO3 （A=Sr, La; B=Mn, Fe, Co） were prepared by citric acid method. The degradation of water-solubilized dyes was carried out using the mixed oxides as photocatalyst. The surface absorb...Perovskite-type complex oxides ABO3 （A=Sr, La; B=Mn, Fe, Co） were prepared by citric acid method. The degradation of water-solubilized dyes was carried out using the mixed oxides as photocatalyst. The surface absorbed oxygen was analyzed using X-ray photoelectron spectroscopy （XPS）. The results indicated that there was a relationship between the photocatalytic activity and the content of the surface absorbed oxygen. The higher the content of the surface absorbed oxygen was, the better the performance of the photocatalyst.展开更多
Photocatalytic degradation of gaseous pollutants on Bi-based semiconductors under solar lightirradiation has attracted significant attention.However,their application in gaseous straight-chainalkane purification is st...Photocatalytic degradation of gaseous pollutants on Bi-based semiconductors under solar lightirradiation has attracted significant attention.However,their application in gaseous straight-chainalkane purification is still rare.Here,a series of Bi/BiOBr composites were solvothermally synthe-sized and applied in solar-light-driven photocatalytic degradation of gaseous n-hexane.The charac-terization results revealed that both increasing number of functional groups of alcohol solvent(from methanol and ethylene glycol to glycerol)and solvothermal temperature(from 160 and 180to 200℃)facilitated the in-situ formation of metallic Bi nanospheres on BiOBr nanoplates withexposed(110)facets.Meanwhile,chemical bonding between Bi and BiOBr was observed on theseexposed facets that resulted in the formation of surface oxygen vacancy.Furthermore,the synergis-tic effect of optimum surface oxygen vacancy on exposed(110)facets led to a high visible light re-sponse,narrow band gap,great photocurrent,low recombination rate of the charge carriers,andstrong·O2-and h*formation,all of which resulted in the highest removal efficiency of 97.4%within120 min of 15 ppmv of n-hexane on Bi/BiOBr.Our findings efficiently broaden the application ofBi-based photocatalysis technology in the purification of gaseous straight-chain pollutants emittedby the petrochemical industry.展开更多
α‐,β‐,δ‐,andγ‐MnO2nanocrystals are successfully prepared.We then evaluated the NH3selective catalytic reduction(SCR)performance of the MnO2catalysts with different phases.The NOx conversion efficiency decrease...α‐,β‐,δ‐,andγ‐MnO2nanocrystals are successfully prepared.We then evaluated the NH3selective catalytic reduction(SCR)performance of the MnO2catalysts with different phases.The NOx conversion efficiency decreased in the order:γ‐MnO2>α‐MnO2>δ‐MnO2>β‐MnO2.The NOx conversion with the use ofγ‐MnO2andα‐MnO2catalysts reached90%in the temperature range of140–200°C,while that based onβ‐MnO2reached only40%at200°C.Theγ‐MnO2andα‐MnO2nanowire crystal morphologies enabled good dispersion of the catalysts and resulted in a relatively high specific surface area.We found thatγ‐MnO2andα‐MnO2possessed stronger reducing abilities and more and stronger acidic sites than the other catalysts.In addition,more chemisorbed oxygen existed on the surface of theγ‐MnO2andα‐MnO2catalysts.Theγ‐MnO2andα‐MnO2catalysts showed excellent performance in the low‐temperature SCR of NO to N2with NH3.展开更多
Surface oxygen vacancy defects of mesoporous CeO_(2)nanosheets assembled microspheres(D-CeO_(2))are engineered by polymer precipitation,hydrothermal and surface hydrogenation strategies.The resultant D-CeO_(2)with a m...Surface oxygen vacancy defects of mesoporous CeO_(2)nanosheets assembled microspheres(D-CeO_(2))are engineered by polymer precipitation,hydrothermal and surface hydrogenation strategies.The resultant D-CeO_(2)with a main pore diameter of 9.3 nm has a large specific surface area(~102.3 m^(2)/g)and high thermal stability.The mesoporous nanosheets assembled microsphere structure prevents the nanosheets from aggregation,which is beneficial to effective mass transfer and shortens the migration distance of charge carriers.After surface hydrogenation,the photoresponse extends to long wavelength region,combing with the band gap from 2.63 eV reduced to 2.39 eV.Under AM 1.5 G radiation,the photocatalytic degradation rate of tetracycline(TC)can be up to 99.99%,which is three times as high as that of pristine CeO_(2)microspheres.The excellent solar-driven photocatalytic performance can be attributed to the efficient surface oxygen vacancy engineering and the mesoporous nanosheets assembled microsphere structure,which narrows the band gap,shortens the migration distance of carriers,promotes the spatial separation of photogenerated electron-hole pairs and favors mass transfer.The strategy provides new insights for fabricating other high-efficient oxide photocatalysts.展开更多
It is known that exposed surface determines material’s performance.WO3 is widely used in gas sensing and its working surface is proposed to control its sensitivity.However,the working surface,or most exposed surface ...It is known that exposed surface determines material’s performance.WO3 is widely used in gas sensing and its working surface is proposed to control its sensitivity.However,the working surface,or most exposed surface with detailed surface structure remain unclear.In this paper,DFT calculation confirmed that oxygen vacancy O-terminated surface is the most exposed hexagonal WO3(001)surface,judging from competitive adsorption of CO and O2,working surface determination for CO sensing and comparison of oxygen vacancy formation ene rgies on different h-WO3(001)surfaces.It is found that DFT can be a useful alternate for exposed surface determination.Our results provide new perspectives and performance explanations for material research.展开更多
A commercial lanthanum oxide was modified into X%-La2O3 samples via partial dissolution and regrowth of crystallites, wherein the X value denotes the weight percent of the initial metal oxide powder dissolved by nitri...A commercial lanthanum oxide was modified into X%-La2O3 samples via partial dissolution and regrowth of crystallites, wherein the X value denotes the weight percent of the initial metal oxide powder dissolved by nitric acid. BET measurements and TEM observations indicate that the 20%-La2O3 sample has an increased specific surface area, relatively thin and small crystallites in size. TPD/TPR profiles also show that the 20%-La2O3 sample has more surface active oxygen than the 0%-La2O3 sample. Among the four X%-La2O3 samples, the highest activity for methane oxidation was obtained over the 20%-La2O3 sample. Therefore, the present work proves that the method of partial dissolution and regrowth of crystallites are effective to modify surface property of lanthanum oxide.展开更多
Formaldehyde(HCHO) and carbon monoxide(CO) are both common air pollutants and hazardous to human body. It is imperative to develop the catalyst that is able to efficiently remove these pollutants. In this work, we act...Formaldehyde(HCHO) and carbon monoxide(CO) are both common air pollutants and hazardous to human body. It is imperative to develop the catalyst that is able to efficiently remove these pollutants. In this work, we activated Pt-MnO_(2)under different conditions for highly active oxidation of HCHO and CO, and the catalyst activated under CO displayed superior performance. A suite of complementary characterizations revealed that the catalyst activated with CO created the highly dispersed Pt nanoparticles to maintain a more positively charged state of Pt, which appropriately weakens the Mn-O bonding strength in the adjacent region of Pt for efficient supply of active oxygen during the reaction. Compared with other catalysts activated under different conditions, the CO-activated Pt-MnO_(2)displays much higher activity for oxidation of HCHO and CO. This research contributes to elucidating the mechanism for regulating the oxidation activity of Pt-based catalyst.展开更多
A novel pulse 18O-16O isotopic exchange (PIE) technique for measurement of the rate of oxygen surface exchange of oxide ion conductors was presented. The technique employs a continuous flow packed-bed micro-reactor lo...A novel pulse 18O-16O isotopic exchange (PIE) technique for measurement of the rate of oxygen surface exchange of oxide ion conductors was presented. The technique employs a continuous flow packed-bed micro-reactor loaded with the oxide powder. The isothermal response to an 18O-enriched pulse passing through the reactor, thereby maintaining chemical equilibrium, is measured by on-line mass spectrometry. Evaluation of the apparent exchange rate follows from the uptake of 18O by the oxide at given reactor residence time and surface area available for exchange. The developed PIE technique is rapid, simple and highly suitable for screening and systematic studies. No rapid heating/quenching steps are required to facilitate 18O tracer anneal or analysis, as in other commonly used techniques based upon oxygen isotopic exchange. Moreover, the relative distribution of the oxygen isotopologues 18O2, 16O18O, and 16O2 in the effluent pulse provides insight into the mechanism of the oxygen exchange reaction. The PIE technique has been demonstrated by measuring the exchange rate of selected oxides with enhanced oxide ionic conductivity in the range of 350?900 oC. Analysis of the experimental data in terms of a model with two consecutive, lumped steps for the isotopic exchange reaction shows that for mixed conductors Ba0.5Sr0.5Co0.8Fe0.2O3-δ(BSCF) and La2NiO4+δ the reaction is limited by the apparent rate of dissociative adsorption of O2 molecules at the oxide surface. For yttria-stabilized zirconia (YSZ), a change-over takes place, from rate-limitations by oxygen incorporation below ∽800 oC to rate-limitations by O2 dissociative adsorption above this temperature. Good agreement is obtained with exchange rates reported for these materials in literature.展开更多
This article discussed the benzoic acid activated carbons which have changed the types and content of acid oxygen-function groups on the surface of activated carbons and their effect on the adsorption for Hg^0 in simu...This article discussed the benzoic acid activated carbons which have changed the types and content of acid oxygen-function groups on the surface of activated carbons and their effect on the adsorption for Hg^0 in simulated flue gas at 140 ℃. These surface acid oxygen function groups were identified by Boehm titration, Fourier transformation infrared spectrum, temperature programmed desorption and X-ray photoelectron spectroscopy. It indicates that the carboxyl, lactone and phenolic were formed when the benzoic acid is loaded on the surface of activated carbons. Among the surface acid oxygen function groups, the carboxyl groups enhance the adsorption capacities of Hg^0 for activated carbons to a greater extent.展开更多
To achieve high energy density in lithium batteries,the construction of lithium-ion/metal hybrid anodes is a promising strategy.In particular,because of the anisotropy of graphite,hybrid anode formed by graphite/Li me...To achieve high energy density in lithium batteries,the construction of lithium-ion/metal hybrid anodes is a promising strategy.In particular,because of the anisotropy of graphite,hybrid anode formed by graphite/Li metal has low transport kinetics and is easy to causes the growth of lithium dendrites and accumulation of dead Li,which seriously affects the cycle life of batteries and even causes safety problems.Here,by comparing graphite with two types of hard carbon,it was found that hybrid anode formed by hard carbon and lithium metal,possessing more disordered mesoporous structure and lithophilic groups,presents better performance.Results indicate that the mesoporous structure provides abundant active site and storage space for dead lithium.With the synergistic effect of this structure and lithophilic functional groups(–COOH),the reversibility of hard carbon/lithium metal hybrid anode is maintained,promoting uniform deposition of lithium metal and alleviating formation of lithium dendrites.The hybrid anode maintains a 99.5%Coulombic efficiency(CE)after 260 cycles at a specific capacity of 500 m Ah/g.This work provides new insights into the hybrid anodes formed by carbon-based materials and lithium metal with high specific energy and fast charging ability.展开更多
Catalysts for CO_(2)value-added conversion have been extensively explored,but there is still a lack of systematic design for catalysts that achieve efficient CO_(2)conversion under mild conditions.Herein,we explored a...Catalysts for CO_(2)value-added conversion have been extensively explored,but there is still a lack of systematic design for catalysts that achieve efficient CO_(2)conversion under mild conditions.Herein,we explored a mesoporous CeO_(2)single-crystal formed with the regulation of ionic liquids,which catalyzed the effective carbonylation reaction with CO_(2)under mild reaction conditions.By altering the synthetic environment,a series of uniform mesoporous CeO_(2)particles with atomically aligned single-crystal frameworks were constructed,which have different surface physicochemical properties and primary aggregation degree.The prepared mesoporous CeO_(2)single-crystal achieved efficient activation of CO_(2)and alcohols at 0.5 MPa CO_(2)and 100℃,and the CeO_(2)-IL-M catalyst shows optimal catalytic performance in the synthesis of ethylene carbonate with 46.22 mmol g^(–1)h^(–1),which was 50.6 times as high as that of the CeO_(2)obtained without ionic liquids.Subsequently,the catalytic pathway and mechanism of carbonylation reaction with CO_(2)on mesoporous CeO_(2)single-crystal were studied via React-IR spectra and C18O_(2)labeling experiments.The research provides a new strategy for controllable nanoscale assembly of mesoporous single-crystal materials and expands the application range of single-crystal materials,aiming to develop novel catalytic materials to meet industrial needs.展开更多
The effects of different outer diameters and surface oxygen contents on the adsorption of heavy metals onto six types of multi-walled carbon nanotubes （MWCNTs） were investigated in an aqueous solution and lead was c...The effects of different outer diameters and surface oxygen contents on the adsorption of heavy metals onto six types of multi-walled carbon nanotubes （MWCNTs） were investigated in an aqueous solution and lead was chosen as a model metal ion. The results indicated that the percentage removal and adsorption capacity of lead remarkably increased with decreasing outer diameter due to larger specific surface area （SSA）. The SSA-normalized maximum adsorption capacity （qJSSA） and SSA-normalized adsorption coefficient （KdSSA） were strongly positively correlated with surface oxygen content, implying that lead adsorption onto MWCNTs significantly increases with the rise of oxygen content and decreases with decreasing SSA. The calculated thermodynamic parameters indicated that adsorption of lead on MWCNTs was endothermic and spontaneous. When the oxygen content of MWCNTs increased from 2.0% to 5.9%, the standard free energy （AGt） became more negative, which implied that the oxygenated functional groups increased the adsorption affinity of MWCNTs for lead. Through calculation of enthalpy （△H0）, AGO and free energy of adsorption （Ea）, lead adsorption onto MWCNTs was recognized as a chemisorption process. The chemical interaction between lead and the phenolic groups of MWCNTs could be one of the main adsorption mechanisms due to highly positive correlations between the phenolic groups and Kd/SSA or qm/SSA.展开更多
To optimize the electronic structure of photocatalyst,a facile one‐step approach is developed for the simultaneous realization of Zn‐doping and surface oxygen vacancies(SOVs)formation on SnO_(2).The Zn‐doped SnO_(2...To optimize the electronic structure of photocatalyst,a facile one‐step approach is developed for the simultaneous realization of Zn‐doping and surface oxygen vacancies(SOVs)formation on SnO_(2).The Zn‐doped SnO_(2)with abundant SOVs exhibits efficient and stable performance for photocatalytic degradation of toluene under both low and high relative humidity.Experimental and theoretical calculations results show that the synergistic effects of Zn‐doping and SOVs on SnO_(2)can considerably boost the charge transfer and separation efficiency.Utilizing the in situ DRIFTS and theoretical calculations methods,it is revealed that the benzene ring of toluene is opened at benzoic acid on the SnO_(2)surface and selectively at benzaldehyde on the Zn‐doped SnO_(2)surface.This implies that Zn‐doped SnO_(2)photocatalysts shorten the pathway of toluene degradation,and toxic intermediates can be significantly inhibited.This work could provide a promising and sustainable route for safe and efficient removal of aromatic VOCs with photocatalytic technology.展开更多
A2B2O7 pyrochlore is a kind of important functional materials for different purposes,which has been investigated extensively by crystallographers and material scientists.However,the catalytic chemistry of this type of...A2B2O7 pyrochlore is a kind of important functional materials for different purposes,which has been investigated extensively by crystallographers and material scientists.However,the catalytic chemistry of this type of special compounds has rarely been documented,though a few researchers have tried to synthesize some pyrochlore compounds with different chemical compositions for a variety of green energy production and air pollution control reactions in the history.With the expectation to help catalysis scientists to get better acquaintance with,and gain deeper understanding on this type of compounds as heterogeneous catalysts,the major publications over the past several decades have been screened and reviewed in this paper,based also on our own experience of studying on this type of catalytic materials.The crystalline phase transformations of the compounds with the change of the A and B site cations,the phase change’s influences on the surface and bulk properties,and their subsequent impact on the catalytic performance for different reactions have been summarized.Furthermore,the future work which needs to be performed to perceive in depth this kind of important materials as catalysts has been proposed and suggested.We trust that this short review contains valuable information,which will provide great help for people to get better cognition for A2 B2 O7 pyrochlore compounds,and assist them to develop better catalysts for various reactions.展开更多
CeO2,Ce1–xZrxO2,and Ce1–xYxO2–δ(x=0.25,0.50,0.75,and 1.00)have been rapidly synthesized to estimate their catalytic behavior in decomposing CH3SH.The role of oxygen vacancies,and the relationship between the oxyge...CeO2,Ce1–xZrxO2,and Ce1–xYxO2–δ(x=0.25,0.50,0.75,and 1.00)have been rapidly synthesized to estimate their catalytic behavior in decomposing CH3SH.The role of oxygen vacancies,and the relationship between the oxygen species and catalytic properties of CeO2 and Zr‐doped and Y‐doped ceria‐based materials are investigated in detail.Combining the observed catalytic performance with the characterization results,it can be deemed that surface lattice oxygen plays a critical role in methanethiol catalytic conversion over cerium oxides.Ce0.75Zr0.25O2 shows higher catalytic activity for CH3SH decomposition due to the large amount of surface lattice oxygen,readily available oxygen species,and excellent redox properties.Ce0.75Y0.25O2–δdisplays better catalytic stability owing to the greater number of oxygen vacancies that would promote bulk lattice oxygen migration to the surface of the catalyst in order to replenish surface lattice oxygen.In addition,the results show that the difference in chemical valence between Ce and the heteroatoms would strongly influence the amount of surface lattice oxygen as well as the mobility of bulk‐phase oxygen in these catalysts,thus affecting their activity and stability.展开更多
基金supported by the National Natural Science Foundation(No.51678291)the Basic Science(Natural Science)Research in Higher Education in Jiangsu Province(No.23KJA610003)the High-level Scientific Research Foundation for the introduction of talent in Nanjing Institute of Technology(No.YKJ201999)。
文摘Most studies have shown that oxygen vacancies on Ce_(x)Zr_(1-x)O_(2) solid solution are important for enhancing the catalytic oxidation performance.However,a handful of studies investigated the different roles of surface and subsurface oxygen vacancies on the performance and mechanisms of catalysts.Herein,a series of zirconium doping on CeO_(2) samples(CeO_(2),Ce_(0.95)Zr_(0.05)O_(2),and Ce_(0.8)5Zr_(0.15)O_(2))with various surface-to-subsurface oxygen vacancies ratios have been synthesized and applied in toluene catalytic oxidation.The obtained Ce_(0.95)Zr_(0.05)O_(2) exhibits an excellent catalytic performance with a 90%toluene conversion at 295℃,which is 68℃lower than that of CeO_(2).Additionally,the obtained Ce_(0.95)Zr_(0.05)O_(2)catalyst also exhibited good catalytic stability and water resistance.The XRD and HRTEM results show that Zr ions are incorporated into CeO_(2) lattice,forming Ce_(x)Zr_(1-x)O_(2) solid solution.Temperature-programmed experiments reveal that Ce_(0.95)Zr_(0.05)O_(2) shows excellent lowtemperature reducibility and abundant surface oxygen species.In-situ DRIFTS tests were used to probe the reaction mechanism,and the function of Zr doping in promoting the activation of oxygen was further determined.Density functional theory(DFT)calculations indicate that the vacancy formation energy and O_(2) adsorption energy are both lower on Ce_(0.95)Zr_(0.05)O_(2),confirming the reason for its superior catalytic performance.
基金supported by the National Natural Science Foundation of China(Nos.22025604,22106171,21936005,and 21976196)the Jinan“20 Universities”Funding Project(No.2020GXRC027)。
文摘Formaldehyde(HCHO)is a common indoor pollutant that is detrimental to human health.Its efficient removal has become an urgent demand to reduce the public health risk.In this work,Ag-MnO_(x)-based catalysts were prepared and activated under different atmosphere(i.e.,air,hydrogen(H_(2))and carbon monoxide(CO))for efficient oxidation of HCHO.The catalyst activated with CO(Ag/Mn-CO)displayed the highest activity among the tested samples with 90% conversion at 100℃ under a gas space velocity of 75,000 mL/(g_(cat)·hr).Complementary characterizations demonstrate that CO reduction treatment resulted in synergically regulated content of surface oxygen on support to adsorb/activate HCHO and size of Ag particle to dissociate oxygen to oxidize the adsorbed HCHO.In contrast,other catalysts lack for either abundant surface oxygen species or metallic silver with the appropriate particle size,so that the integrate activity is limited by one specific reaction step.This study contributes to elucidating the mechanisms regulating the oxidation activity of Ag-based catalysts.
基金supported by the National Natural Science Foundation of China(No.22278041)the Foundation of State Key Laboratory of High-efficiency Utilization of Coal and Green Chemical Engineering(No.2022-K78)+1 种基金Jiangsu Province Key Laboratory of Fine Petrochemical Engineering(No.KF2107)the Advanced Catalysis and Green Manufacturing Collab-orative Innovation Center(No.ACGM2022-10-07)。
文摘Herein,a series of manganese oxide catalysts with different valences(Mn_(3)O_(4),Mn_(2)O_(3),and MnO_(2))were designed and synthesized for the synthesis of ethylene urea(EU)from ethylenediamine(EDA)and carbon dioxide(CO_(2)).With a maximal EDA conversion of 82%and EU selectivity of 99%at 160℃ for 2 h,Mn_(2)O_(3) catalysts had the best catalytic activity among them,which was superior to the reported catalysts.In the following order:Mn_(2)O_(3)>MnO_(2)>Mn_(3)O_(4),the catalytic activity for the synthesis of EU from CO_(2) and EDA decreased.Further characterization showed the Mn_(2)O_(3) catalyst possessed a greater Mn^(3+)/Mn4+ratio and more surface oxygen vacancies than the MnO_(2) and Mn_(3)O_(4),which improved its capacity to adsorb and activate CO_(2) and EDA.After four recycling runs,the EDA conversion slightly declined from 82%to 56%on Mn_(2)O_(3) catalyst,while no obvious change in EU selectivity was observed.The loss of surface Ov contents and Mn^(3+)proportion were concluded as main reasons for the decrease in catalytic activity over Mn_(2)O_(3) catalyst.This work demonstrated a metal oxide catalyst that was efficient in producing EU from CO_(2) and EDA.
基金supported by the National Natural Science Foundation of China(Nos.22025604 and 22276204)the National Key R&D Program of China(Nos.2023YFC3708401 and 2022YFC3800404).
文摘To develop efficient catalysts for ambient carbon monoxide(CO)oxidation is significant for indoor air purification and also for many industrial applications.In this work,the catalytic activity for CO oxidation were enhanced by tuning the metal-support interaction of Ru/CeO_(2)catalysts.A series of Ru/CeO_(2)catalysts were synthesized by an impregnation method with calcination at 100,200,400 and 600℃,respectively,to regulate the Ru-CeO_(2)interaction.We discovered that low temperature calcination(100℃)induced more Ru-O-Ce bonds and stronger Ru-CeO_(2)interaction,while high temperature calcination(≥400℃)caused the agglomeration of Ru species with more Ru-O-Ru bonds and weaker Ru-CeO_(2)interaction,resulting in the lower redox capacity of these catalysts,as well as lower catalytic activity for CO oxidation.Only calcination at moderate 200℃ can induce the moderate interaction between Ru species and CeO_(2)support,which can keep the high dispersion of RuO_(x)species with the high redox capacity,thus leading to complete elimination of 500 ppm CO at room temperature on Ru/Ce-200 catalyst.
文摘Co3O4/SiO2 catalysts for CO oxidation were prepared by conventional incipient wetness impregnation followed by calcination at various temperatures. Their structures were char- acterized with X-ray diffraction （XRD）, laser Raman spectroscopy, X-ray photoelectron spectroscopy （XPS）, temperature-programmed reduction （TPR） and X-ray absorption fine structure （XAFS） spectroscopy. Both XRD and Raman spectroscopy only detect the existence of Co3O4 crystallites in all catalysts. However, XPS results indicate that excess Co2＋ ions are present on the surface of Co3O4 in Co3O4（200）/Si02 as compared with bulk Co3O4. Meanwhile, TPR results suggest the presence of surface oxygen vacancies on Co3O4 in Co3O4（200）/SiO2, and XAFS results demonstrate that Co3O4 in Co3O4（200）/SIO2 contains excess Co2＋. Increasing calcination temperature results in oxidation of excess Co2＋ and the decrease of the concentration of surface oxygen vacancies, consequently the for- mation of stoichiometric Co3O4 on supported catalysts. Among all Co3O4/SiO2 catalysts, Co3O4（200）/SiO2 exhibits the best catalytic performance towards CO oxidation, demonstrating that excess Co2＋ and surface oxygen vacancies can enhance the catalytic activity of Co3O4 towards CO oxidation. These results nicely demonstrate the effect of calcination temperature on the structure and catalytic performance towards CO oxidation of silicasupported Co3O4 catalysts and highlight the important role of surface oxygen vacancies on Co3O4.
基金the National Natural Science Foundation of China (20671069)
文摘Perovskite-type complex oxides ABO3 （A=Sr, La; B=Mn, Fe, Co） were prepared by citric acid method. The degradation of water-solubilized dyes was carried out using the mixed oxides as photocatalyst. The surface absorbed oxygen was analyzed using X-ray photoelectron spectroscopy （XPS）. The results indicated that there was a relationship between the photocatalytic activity and the content of the surface absorbed oxygen. The higher the content of the surface absorbed oxygen was, the better the performance of the photocatalyst.
文摘Photocatalytic degradation of gaseous pollutants on Bi-based semiconductors under solar lightirradiation has attracted significant attention.However,their application in gaseous straight-chainalkane purification is still rare.Here,a series of Bi/BiOBr composites were solvothermally synthe-sized and applied in solar-light-driven photocatalytic degradation of gaseous n-hexane.The charac-terization results revealed that both increasing number of functional groups of alcohol solvent(from methanol and ethylene glycol to glycerol)and solvothermal temperature(from 160 and 180to 200℃)facilitated the in-situ formation of metallic Bi nanospheres on BiOBr nanoplates withexposed(110)facets.Meanwhile,chemical bonding between Bi and BiOBr was observed on theseexposed facets that resulted in the formation of surface oxygen vacancy.Furthermore,the synergis-tic effect of optimum surface oxygen vacancy on exposed(110)facets led to a high visible light re-sponse,narrow band gap,great photocurrent,low recombination rate of the charge carriers,andstrong·O2-and h*formation,all of which resulted in the highest removal efficiency of 97.4%within120 min of 15 ppmv of n-hexane on Bi/BiOBr.Our findings efficiently broaden the application ofBi-based photocatalysis technology in the purification of gaseous straight-chain pollutants emittedby the petrochemical industry.
基金supported by the National Natural Science Foundation of China(51502221)~~
文摘α‐,β‐,δ‐,andγ‐MnO2nanocrystals are successfully prepared.We then evaluated the NH3selective catalytic reduction(SCR)performance of the MnO2catalysts with different phases.The NOx conversion efficiency decreased in the order:γ‐MnO2>α‐MnO2>δ‐MnO2>β‐MnO2.The NOx conversion with the use ofγ‐MnO2andα‐MnO2catalysts reached90%in the temperature range of140–200°C,while that based onβ‐MnO2reached only40%at200°C.Theγ‐MnO2andα‐MnO2nanowire crystal morphologies enabled good dispersion of the catalysts and resulted in a relatively high specific surface area.We found thatγ‐MnO2andα‐MnO2possessed stronger reducing abilities and more and stronger acidic sites than the other catalysts.In addition,more chemisorbed oxygen existed on the surface of theγ‐MnO2andα‐MnO2catalysts.Theγ‐MnO2andα‐MnO2catalysts showed excellent performance in the low‐temperature SCR of NO to N2with NH3.
基金the support of this research by the National Natural Science Foundation of China(No.21871078)the Natural Science Foundation of Heilongjiang Province(Nos.JQ2019B001,LH2019B014)the Youth Science and Technology Innovation Team Project of Heilongjiang Province(No.2018-KYYWF-1593)。
文摘Surface oxygen vacancy defects of mesoporous CeO_(2)nanosheets assembled microspheres(D-CeO_(2))are engineered by polymer precipitation,hydrothermal and surface hydrogenation strategies.The resultant D-CeO_(2)with a main pore diameter of 9.3 nm has a large specific surface area(~102.3 m^(2)/g)and high thermal stability.The mesoporous nanosheets assembled microsphere structure prevents the nanosheets from aggregation,which is beneficial to effective mass transfer and shortens the migration distance of charge carriers.After surface hydrogenation,the photoresponse extends to long wavelength region,combing with the band gap from 2.63 eV reduced to 2.39 eV.Under AM 1.5 G radiation,the photocatalytic degradation rate of tetracycline(TC)can be up to 99.99%,which is three times as high as that of pristine CeO_(2)microspheres.The excellent solar-driven photocatalytic performance can be attributed to the efficient surface oxygen vacancy engineering and the mesoporous nanosheets assembled microsphere structure,which narrows the band gap,shortens the migration distance of carriers,promotes the spatial separation of photogenerated electron-hole pairs and favors mass transfer.The strategy provides new insights for fabricating other high-efficient oxide photocatalysts.
基金supported by National Natural Science Foundation of China(Nos.61971252,20703027)Excellent Youth Fund of Shandong Province(No.ZR201709200070)+2 种基金Foundation of Shandong Educational Committee(No.J09LB06)Shandong excellent young scientist research award fund(No.BS2011NJ004)open project of Shanghai Key Laboratory of Rare Earth Functional Materials。
文摘It is known that exposed surface determines material’s performance.WO3 is widely used in gas sensing and its working surface is proposed to control its sensitivity.However,the working surface,or most exposed surface with detailed surface structure remain unclear.In this paper,DFT calculation confirmed that oxygen vacancy O-terminated surface is the most exposed hexagonal WO3(001)surface,judging from competitive adsorption of CO and O2,working surface determination for CO sensing and comparison of oxygen vacancy formation ene rgies on different h-WO3(001)surfaces.It is found that DFT can be a useful alternate for exposed surface determination.Our results provide new perspectives and performance explanations for material research.
文摘A commercial lanthanum oxide was modified into X%-La2O3 samples via partial dissolution and regrowth of crystallites, wherein the X value denotes the weight percent of the initial metal oxide powder dissolved by nitric acid. BET measurements and TEM observations indicate that the 20%-La2O3 sample has an increased specific surface area, relatively thin and small crystallites in size. TPD/TPR profiles also show that the 20%-La2O3 sample has more surface active oxygen than the 0%-La2O3 sample. Among the four X%-La2O3 samples, the highest activity for methane oxidation was obtained over the 20%-La2O3 sample. Therefore, the present work proves that the method of partial dissolution and regrowth of crystallites are effective to modify surface property of lanthanum oxide.
基金supported by the National Natural Science Foundation of China (Nos. 22025604, 21976196, 21972170 and 22072184)。
文摘Formaldehyde(HCHO) and carbon monoxide(CO) are both common air pollutants and hazardous to human body. It is imperative to develop the catalyst that is able to efficiently remove these pollutants. In this work, we activated Pt-MnO_(2)under different conditions for highly active oxidation of HCHO and CO, and the catalyst activated under CO displayed superior performance. A suite of complementary characterizations revealed that the catalyst activated with CO created the highly dispersed Pt nanoparticles to maintain a more positively charged state of Pt, which appropriately weakens the Mn-O bonding strength in the adjacent region of Pt for efficient supply of active oxygen during the reaction. Compared with other catalysts activated under different conditions, the CO-activated Pt-MnO_(2)displays much higher activity for oxidation of HCHO and CO. This research contributes to elucidating the mechanism for regulating the oxidation activity of Pt-based catalyst.
文摘A novel pulse 18O-16O isotopic exchange (PIE) technique for measurement of the rate of oxygen surface exchange of oxide ion conductors was presented. The technique employs a continuous flow packed-bed micro-reactor loaded with the oxide powder. The isothermal response to an 18O-enriched pulse passing through the reactor, thereby maintaining chemical equilibrium, is measured by on-line mass spectrometry. Evaluation of the apparent exchange rate follows from the uptake of 18O by the oxide at given reactor residence time and surface area available for exchange. The developed PIE technique is rapid, simple and highly suitable for screening and systematic studies. No rapid heating/quenching steps are required to facilitate 18O tracer anneal or analysis, as in other commonly used techniques based upon oxygen isotopic exchange. Moreover, the relative distribution of the oxygen isotopologues 18O2, 16O18O, and 16O2 in the effluent pulse provides insight into the mechanism of the oxygen exchange reaction. The PIE technique has been demonstrated by measuring the exchange rate of selected oxides with enhanced oxide ionic conductivity in the range of 350?900 oC. Analysis of the experimental data in terms of a model with two consecutive, lumped steps for the isotopic exchange reaction shows that for mixed conductors Ba0.5Sr0.5Co0.8Fe0.2O3-δ(BSCF) and La2NiO4+δ the reaction is limited by the apparent rate of dissociative adsorption of O2 molecules at the oxide surface. For yttria-stabilized zirconia (YSZ), a change-over takes place, from rate-limitations by oxygen incorporation below ∽800 oC to rate-limitations by O2 dissociative adsorption above this temperature. Good agreement is obtained with exchange rates reported for these materials in literature.
文摘This article discussed the benzoic acid activated carbons which have changed the types and content of acid oxygen-function groups on the surface of activated carbons and their effect on the adsorption for Hg^0 in simulated flue gas at 140 ℃. These surface acid oxygen function groups were identified by Boehm titration, Fourier transformation infrared spectrum, temperature programmed desorption and X-ray photoelectron spectroscopy. It indicates that the carboxyl, lactone and phenolic were formed when the benzoic acid is loaded on the surface of activated carbons. Among the surface acid oxygen function groups, the carboxyl groups enhance the adsorption capacities of Hg^0 for activated carbons to a greater extent.
基金Financial support from the National Natural Science Foundation of China (22075320)。
文摘To achieve high energy density in lithium batteries,the construction of lithium-ion/metal hybrid anodes is a promising strategy.In particular,because of the anisotropy of graphite,hybrid anode formed by graphite/Li metal has low transport kinetics and is easy to causes the growth of lithium dendrites and accumulation of dead Li,which seriously affects the cycle life of batteries and even causes safety problems.Here,by comparing graphite with two types of hard carbon,it was found that hybrid anode formed by hard carbon and lithium metal,possessing more disordered mesoporous structure and lithophilic groups,presents better performance.Results indicate that the mesoporous structure provides abundant active site and storage space for dead lithium.With the synergistic effect of this structure and lithophilic functional groups(–COOH),the reversibility of hard carbon/lithium metal hybrid anode is maintained,promoting uniform deposition of lithium metal and alleviating formation of lithium dendrites.The hybrid anode maintains a 99.5%Coulombic efficiency(CE)after 260 cycles at a specific capacity of 500 m Ah/g.This work provides new insights into the hybrid anodes formed by carbon-based materials and lithium metal with high specific energy and fast charging ability.
文摘Catalysts for CO_(2)value-added conversion have been extensively explored,but there is still a lack of systematic design for catalysts that achieve efficient CO_(2)conversion under mild conditions.Herein,we explored a mesoporous CeO_(2)single-crystal formed with the regulation of ionic liquids,which catalyzed the effective carbonylation reaction with CO_(2)under mild reaction conditions.By altering the synthetic environment,a series of uniform mesoporous CeO_(2)particles with atomically aligned single-crystal frameworks were constructed,which have different surface physicochemical properties and primary aggregation degree.The prepared mesoporous CeO_(2)single-crystal achieved efficient activation of CO_(2)and alcohols at 0.5 MPa CO_(2)and 100℃,and the CeO_(2)-IL-M catalyst shows optimal catalytic performance in the synthesis of ethylene carbonate with 46.22 mmol g^(–1)h^(–1),which was 50.6 times as high as that of the CeO_(2)obtained without ionic liquids.Subsequently,the catalytic pathway and mechanism of carbonylation reaction with CO_(2)on mesoporous CeO_(2)single-crystal were studied via React-IR spectra and C18O_(2)labeling experiments.The research provides a new strategy for controllable nanoscale assembly of mesoporous single-crystal materials and expands the application range of single-crystal materials,aiming to develop novel catalytic materials to meet industrial needs.
基金supported by the National High Technology Research and Development Program (863) of China (No.2007AA06Z334)the Scholarship Award for Excellent Doctoral Student granted by Ministry of Education and the Shanghai Jiao Tong University Innovation Fund for Postgraduates+1 种基金the State Key Laboratory of Pollution Control and Resource Reuse Foundation (No. PCRRY11009)the Program for Young Excellent Talents at Tongji University (No. 2010KJ026)
文摘The effects of different outer diameters and surface oxygen contents on the adsorption of heavy metals onto six types of multi-walled carbon nanotubes （MWCNTs） were investigated in an aqueous solution and lead was chosen as a model metal ion. The results indicated that the percentage removal and adsorption capacity of lead remarkably increased with decreasing outer diameter due to larger specific surface area （SSA）. The SSA-normalized maximum adsorption capacity （qJSSA） and SSA-normalized adsorption coefficient （KdSSA） were strongly positively correlated with surface oxygen content, implying that lead adsorption onto MWCNTs significantly increases with the rise of oxygen content and decreases with decreasing SSA. The calculated thermodynamic parameters indicated that adsorption of lead on MWCNTs was endothermic and spontaneous. When the oxygen content of MWCNTs increased from 2.0% to 5.9%, the standard free energy （AGt） became more negative, which implied that the oxygenated functional groups increased the adsorption affinity of MWCNTs for lead. Through calculation of enthalpy （△H0）, AGO and free energy of adsorption （Ea）, lead adsorption onto MWCNTs was recognized as a chemisorption process. The chemical interaction between lead and the phenolic groups of MWCNTs could be one of the main adsorption mechanisms due to highly positive correlations between the phenolic groups and Kd/SSA or qm/SSA.
文摘To optimize the electronic structure of photocatalyst,a facile one‐step approach is developed for the simultaneous realization of Zn‐doping and surface oxygen vacancies(SOVs)formation on SnO_(2).The Zn‐doped SnO_(2)with abundant SOVs exhibits efficient and stable performance for photocatalytic degradation of toluene under both low and high relative humidity.Experimental and theoretical calculations results show that the synergistic effects of Zn‐doping and SOVs on SnO_(2)can considerably boost the charge transfer and separation efficiency.Utilizing the in situ DRIFTS and theoretical calculations methods,it is revealed that the benzene ring of toluene is opened at benzoic acid on the SnO_(2)surface and selectively at benzaldehyde on the Zn‐doped SnO_(2)surface.This implies that Zn‐doped SnO_(2)photocatalysts shorten the pathway of toluene degradation,and toxic intermediates can be significantly inhibited.This work could provide a promising and sustainable route for safe and efficient removal of aromatic VOCs with photocatalytic technology.
基金Project supported by the National Natural Science Foundation of China(21962009,21567016,21666020)Natural Science Foundation of Jiangxi Province(20181ACB20005,20171BAB213013,20181BAB203017)Key Laboratory Foundation of Jiangxi Province for Environment and Energy Catalysis(20181BCD40004)。
文摘A2B2O7 pyrochlore is a kind of important functional materials for different purposes,which has been investigated extensively by crystallographers and material scientists.However,the catalytic chemistry of this type of special compounds has rarely been documented,though a few researchers have tried to synthesize some pyrochlore compounds with different chemical compositions for a variety of green energy production and air pollution control reactions in the history.With the expectation to help catalysis scientists to get better acquaintance with,and gain deeper understanding on this type of compounds as heterogeneous catalysts,the major publications over the past several decades have been screened and reviewed in this paper,based also on our own experience of studying on this type of catalytic materials.The crystalline phase transformations of the compounds with the change of the A and B site cations,the phase change’s influences on the surface and bulk properties,and their subsequent impact on the catalytic performance for different reactions have been summarized.Furthermore,the future work which needs to be performed to perceive in depth this kind of important materials as catalysts has been proposed and suggested.We trust that this short review contains valuable information,which will provide great help for people to get better cognition for A2 B2 O7 pyrochlore compounds,and assist them to develop better catalysts for various reactions.
基金supported by the National Natural Science Foundation of China (21667016, 21267011, U1402233)~~
文摘CeO2,Ce1–xZrxO2,and Ce1–xYxO2–δ(x=0.25,0.50,0.75,and 1.00)have been rapidly synthesized to estimate their catalytic behavior in decomposing CH3SH.The role of oxygen vacancies,and the relationship between the oxygen species and catalytic properties of CeO2 and Zr‐doped and Y‐doped ceria‐based materials are investigated in detail.Combining the observed catalytic performance with the characterization results,it can be deemed that surface lattice oxygen plays a critical role in methanethiol catalytic conversion over cerium oxides.Ce0.75Zr0.25O2 shows higher catalytic activity for CH3SH decomposition due to the large amount of surface lattice oxygen,readily available oxygen species,and excellent redox properties.Ce0.75Y0.25O2–δdisplays better catalytic stability owing to the greater number of oxygen vacancies that would promote bulk lattice oxygen migration to the surface of the catalyst in order to replenish surface lattice oxygen.In addition,the results show that the difference in chemical valence between Ce and the heteroatoms would strongly influence the amount of surface lattice oxygen as well as the mobility of bulk‐phase oxygen in these catalysts,thus affecting their activity and stability.
