In this work, the influence of trivalent rare-earth dopants（Sm and La） on the structure-activity properties of CeO2 was thoroughly studied for diesel soot oxidation. For this, an optimized 40% of Sm and La was incor...In this work, the influence of trivalent rare-earth dopants（Sm and La） on the structure-activity properties of CeO2 was thoroughly studied for diesel soot oxidation. For this, an optimized 40% of Sm and La was incorporated into the CeO2 using a facile coprecipitation method from ultra-high dilute aqueous solutions. A systematic physicochemical characterization was carried out using X-ray diffraction（XRD）, transmission electron microscopy（TEM）, Brumauer-Emmett-teller method（BET） surface area, X-ray photoelectron spectroscopy（XPS）, Raman, and H2-temperature programmed reduction（TPR） techniques. The soot oxidation efficiency of the catalysts was investigated using a thermogravimetric method. The XRD results suggested the formation of nanocrystalline single phase CeO2-Sm2O3 and CeO2-La2O3 solid solutions. The Sm- and La-doped CeO2 materials exhibited smaller crystallite size and higher BET surface area compared with the pure CeO2. Owing to the difference in the oxidation states of the dopants（Sm3＋ and La3＋） and the Ce4＋, a number of oxygen vacancies were generated in CeO2-Sm2O3 and CeO2-La2O3 samples. The H2-TPR studies evidenced the improved reducible nature of the CeO2-Sm2O3 and CeO2-La2O3 samples compared with the CeO2. It was found that the addition of Sm and La to the CeO2 outstandingly enhanced its catalytic efficiency for the oxidation of diesel soot. The observed 50% soot conversion temperatures for the CeO2-Sm2O3, CeO2-La2O3 and CeO2 were ~790, 843 and 864 K（loose contact）, respectively, and similar activity order was also found under the tight contact condition. The high soot oxidation efficacy of the CeO2-Sm2O3 sample was attributed to numerous catalytically favourable properties, like smaller crystallite size, larger surface area, abundant oxygen vacancies, and superior reducible nature.展开更多
Catalytic oxidation of toluene over noble metal catalysts is a representative reaction for elimination of volatile organic compounds(VOCs).However,to fully understand the activation of molecular oxygen and the role of...Catalytic oxidation of toluene over noble metal catalysts is a representative reaction for elimination of volatile organic compounds(VOCs).However,to fully understand the activation of molecular oxygen and the role of active oxygen species generated in this reaction is still a challenging target.Herein,MgO nanosheets and single-atom Pt loaded MgO(Pt SA/MgO)nanosheets were synthesized and used as catalysts in toluene oxidation.The activation process of molecular oxygen and oxidation performance on the two catalysts were contrastively investigated.The Pt SA/MgO exhibited significantly enhanced catalytic activity compared to MgO.The oxygen vacancies can be easily generated on the Pt SA/MgO surface,which facilitate the activation of molecular oxygen and the formation of active oxygen species.Based on the experimental data and theoretical calculations,an active oxygen species promoted oxidation mechanism for toluene was proposed.In the presence of H2O,the molecular oxygen is more favorable to be dissociated to generate•OH on the oxygen vacancies of the Pt SA/MgO surface,which is the dominant active oxygen species.We anticipate that this work may shed light on further investigation of t10.1007/s12274-020-2765-1he oxidation mechanism of toluene and other VOCs over noble metal catalysts.展开更多
Aromatic ring-opening process is well recognized as the rate-determining step for catalytic toluene degradation. In photocatalytic toluene degradation, the toxic intermediates w让h harmful effects may be generated. To...Aromatic ring-opening process is well recognized as the rate-determining step for catalytic toluene degradation. In photocatalytic toluene degradation, the toxic intermediates w让h harmful effects may be generated. To clarify the precise reaction mechanism and control the toxic intermediates generation, a closely combined in situ DRIFTS and DFT calculation is utilized to address these important issues. We construct the BiOCl w让h oxygen vacancies (OVs) and reveal the structure of OVs. The defect level caused by oxygen vacancies could promote the light adsorption and charge separation, which further boosts the activation of ring-opening species and enhances the generation process of free radicals. The reaction energy barriers of four possible ring-opening processes on defective BiOCl (OVBOC) are all declined in comparison with perfect BiOCl (BOC). The existence of oxygen vacancies could smooth the ratedetermining step so the ring-opening efficiency of photocatalytic toluene degradation is highly increased. Most importantly, the methyl species would be further oxidized and tend to open the benzene-ring at benzoic acid on BOC while the ring would be broken at the benzyl alcohol on OVBOC. These results indicate that the toluene degradation pathway is shortened via the surface OVs, which enables the production of radicals with high oxidation capability for the accelerated chain scission of the ring-opening intermediates. Finally, the efficiency of the key ring-opening process could be enormously improved and toxic intermediates are effectively restrained. The present work could provide new insights into the design of high-performance photocatalysts for efficient and safe degradation of VOCs in air.展开更多
The CuO/CeO2 catalysts were investigated by means of X-ray diffraction （XRD）, laser Raman spectroscopy （LRS）, X-ray photoelectronic spectroscopy （XPS）, temperature-programmed reduction （TPR）, in situ Fourier t...The CuO/CeO2 catalysts were investigated by means of X-ray diffraction （XRD）, laser Raman spectroscopy （LRS）, X-ray photoelectronic spectroscopy （XPS）, temperature-programmed reduction （TPR）, in situ Fourier transform infrared spectroscopy （FTIR） and NO＋CO reaction. The results revealed that the low temperature （〈150℃） catalytic performances were enhanced for CO pretreated samples. During CO pretreatment, the surface Cu＋/Cu0 and oxygen vacancies on ceria surface were present. The low va- lence copper species activated the adsorbed CO and surface oxygen vacancies facilitated the NO dissociation. These effects in turn led to higher activities of CuO/CeO2 for NO reduction. The current study provided helpful understandings of active sites and reaction mechanism in NO＋CO reaction.展开更多
Lithium-rich layered oxides always suffer from low initial Coulombic efficiency,poor rate capability and rapid voltage fading.Herein,engineering oxygen vacancies in hierarchically Li1.2Mn0.54Ni0.13Co0.13O2 porous micr...Lithium-rich layered oxides always suffer from low initial Coulombic efficiency,poor rate capability and rapid voltage fading.Herein,engineering oxygen vacancies in hierarchically Li1.2Mn0.54Ni0.13Co0.13O2 porous microspheres(L@S)is carried out to suppress the formation of irreversible Li20 during the initial discharge process and improve the Li+diffusion kinetics and structural stability of the cathode mateiral.As a result,the prepared L@S cathode delivers high initial Coulombic efficiency of 92.3%and large specific capacity of 292.6 mA h g^-1 at 0.1 C.More importantly,a large reversible capacity of 222 mA h g^-1 with a capacity retention of95.7%can be obtained after 100 cycles at 10 C.Even cycled at ultrahigh rate of 20 C,the L@S cathode can deliver stable reversible capacity of 153 mA h g^-1 after 100 cycles.Moreover,the full cell using L@S as cathode and Li4 Ti5 O12 as anode exhibits a relatively high reversible capacity of 141 mA h g^-1 with an outstanding voltage retention of 97%after 400 cycles at a large current density of 3 C.These results may shed light on the improvement of electrochemical performances of lithiumrich layered oxides via the multiscale coordinated design based on atomic defects,microstructure and composition.展开更多
Refractory organic pollutants in water threaten human health and environmental safety,and advanced oxidation processes (AOPs) are effective for the degradation of these pollutants.Catalysts play vital role in AOPs,and...Refractory organic pollutants in water threaten human health and environmental safety,and advanced oxidation processes (AOPs) are effective for the degradation of these pollutants.Catalysts play vital role in AOPs,and Ce-based catalysts have exhibited excellent performance.Recently,the development and application of Ce-based catalysts in various AOPs have been reported.Our study conducts the first review in this rapid growing field.This paper clarifies the variety and properties of Ce-based catalysts.Their applications in different AOP systems (catalytic ozonation,photodegradation,Fenton-like reactions,sulfate radicalbased AOPs,and catalytic sonochemistry) are discussed.Different Ce-based catalysts suit different reaction systems and produce different active radicals.Finally,future research directions of Ce-based catalysts in AOP systems are suggested.展开更多
Dielectric barrier discharge（DBD） plasma is considered to be a promising method to synthesize solid catalysts. In this work, DBD plasma was used to synthesize a nitrogen‐vacancy‐doped g‐C3N4 catalyst in situ for ...Dielectric barrier discharge（DBD） plasma is considered to be a promising method to synthesize solid catalysts. In this work, DBD plasma was used to synthesize a nitrogen‐vacancy‐doped g‐C3N4 catalyst in situ for the first time. X‐ray diffraction, N2 adsorption, ultraviolet–visible spectroscopy, scanning electron microscopy, transmission electron microscopy, X‐ray photoelectron spectrosco‐py, electrochemical impedance spectroscopy, electron paramagnetic resonance, O2 tempera‐ture‐programmed desorption, and photoluminescence were used to characterize the obtained cat‐alysts. The photocatalytic H2O2 production ability of the as‐prepared catalyst was investigated. The results show that plasma treatment influences the morphology, structure, and optical properties of the as‐prepared catalyst. Nitrogen vacancies are active centers, which can adsorb reactant oxygen molecules, trap photoelectrons, and promote the transfer of photoelectrons from the catalyst to the adsorbed oxygen molecules for the subsequent reduction reaction. This work provides a new strat‐egy for synthesizing g‐C3N4‐based catalysts.展开更多
Cerium oxide(CeO_(2)),one of the most significant rare-earth oxides,has attracted considerable interest over the past decades.This is primarily due to the ease in Ce^(3+)/Ce^(4+)redox ability as well as other factors ...Cerium oxide(CeO_(2)),one of the most significant rare-earth oxides,has attracted considerable interest over the past decades.This is primarily due to the ease in Ce^(3+)/Ce^(4+)redox ability as well as other factors that affect the efficacy of CeO_(2)and CeO_(2)-based materials.CeO_(2)and CeO_(2)-based materials have shown enhanced responses in catalytic and photocatalytic activities for environmental and biological applications.In addition,the formation of Ce^(3+)and oxygen vacancies in CeO_(2)has aided in enhancing CeO_(2)activities.In order to produce oxygen-deficient CeO_(2)and CeO_(2)-based materials,a variety of synthesis methods were used and are highlighted in this review.Therefore,this review compiles and discusses the mechanisms that involve oxygen vacancies,defects,and Ce^(3+)formation for environmental applications,such as photocatalytic dye degradation,photocatalytic CO_(2)reduction,and non-colored pollutants removal.The biological applications of CeO_(2),such as antioxidant enzyme mimetic,antioxidant reactive oxygen species/reactive nitrogen species,and antimicrobial activities,are also discussed.Additionally,future prospects are also suggested for future development and detailed investigations.展开更多
In this study, CeO2 nanostructures were synthesized by a soft chemical method. A hydrothermal treatment was observed to lead to an interesting morphological transformation of the nanoparticles into homogeneous microsp...In this study, CeO2 nanostructures were synthesized by a soft chemical method. A hydrothermal treatment was observed to lead to an interesting morphological transformation of the nanoparticles into homogeneous microspheres composed of nanosheets with an average thickness of 40 nm. Structural analysis revealed the formation of a single-phase cubic fluorite structure of CeO2 for both samples. A Raman spectroscopic study confirmed the XRD results and furthermore indicated the presence of a large number of oxygen vacancies in the nanosheets. These oxygen vacancies led to room-temperature ferromagnetism （RTFM） of the CeO2 nanosheets with enhanced magnetic characteristics. Amazingly, the nanosheets exhibited substantially greater antibacterial activity than the nanoparticles. This greater antibacte- rial activity was attributed to greater exposure of high-surface-energy polar surfaces and to the presence of oxygen vacancies.展开更多
Oxyge n vaca ncies impla ntation is an efficie nt way to adjust the physical and chemical properties of metal oxide nano materials to meet the requirements for particular applications.Through reasonable defects design...Oxyge n vaca ncies impla ntation is an efficie nt way to adjust the physical and chemical properties of metal oxide nano materials to meet the requirements for particular applications.Through reasonable defects design,oxyge-deficient metal oxides with excellent optical and electrical properties are widely applied for environmental protection and energy uses.This review discusses recent advances in synthetic approaches of oxygervdeficient metal oxides and their applications in photocatalysis,electrocatalysis,and energy storage devices.The perspectives of oxyge n?deficie nt metal oxides for increased en ergy dema nd and en vironme ntal sustai liability are also exami ned.展开更多
Reduction of CO2to solar fuels by artificial photosynthesis technology has attracted considerable attention. However, insufficient separation of charge carriers and weak CO2adsorption hamper the photocatalytic CO2 red...Reduction of CO2to solar fuels by artificial photosynthesis technology has attracted considerable attention. However, insufficient separation of charge carriers and weak CO2adsorption hamper the photocatalytic CO2 reduction activity. Herein, we tackle these challenges by introducing oxygen vacancies (OVs) on the two-dimensional Bi4Ti3O12ultrathin nanosheets via a combined hydrothermal and postreduction process. Selective photodeposition experiment of Pt over Bi4Ti3O12discloses that the ultrathin structure shortens the migration distance of photo-induced electrons from bulk to the surface, benefiting the fast participation in the CO2reduction reaction. The introduction of OVs on ultrathin Bi4Ti3O12 nanosheets leads to enormous amelioration on surface state and electronic structure, thereby resulting in enhanced CO2adsorption, photoabsorption and charge separation efficiency. The photocatalytic experiments uncover that ultrathin Bi4Ti3O12nanosheets with OVs reveal a largely enhanced CO2photoreduction activity for producing CO with a rate of 11.7 lmol g-1h-1in the gas–solid system, 3.2 times higher than that of bulk Bi4Ti3O12. This work not only yields efficient ultrathin photocatalysts with OVs, but also furthers our understanding on enhancing CO2reduction via cooperative tactics.展开更多
MgH_(2) has attracted intensive interests as one of the most promising hydrogen storage materials.Nevertheless,the high desorption temperature,sluggish kinetics,and rapid capacity decay hamper its commercial applicati...MgH_(2) has attracted intensive interests as one of the most promising hydrogen storage materials.Nevertheless,the high desorption temperature,sluggish kinetics,and rapid capacity decay hamper its commercial application.Herein,2D TiO_(2) nanosheets with abundant oxygen vacancies are used to fabricate a flower-like MgH_(2)/TiO_(2) heterostructure with enhanced hydrogen storage performances.Particularly,the onset hydrogen desorption temperature of the MgH_(2)/TiO_(2) heterostructure is lowered down to 180℃(295℃ for blank MgH_(2)).The initial desorption rate of MgH_(2)/TiO_(2) reaches 2.116 wt% min^(-1) at 300℃,35 times of the blank MgH_(2) under the same conditions.Moreover,the capacity retention is as high as 98.5% after 100 cycles at 300℃,remarkably higher than those of the previously reported MgH_(2)-TiO_(2) composites.Both in situ HRTEM observations and ex situ XPS analyses confirm that the synergistic effects from multi-valance of Ti species,accelerated electron transportation caused by oxygen vacancies,formation of catalytic Mg-Ti oxides,and stabilized MgH_(2) NPs confined by TiO_(2) nanosheets contribute to the high stability and kinetically accelerated hydrogen storage performances of the composite.The strategy of using 2D substrates with abundant defects to support nano-sized energy storage materials to build heterostructure is therefore promising for the design of high-performance energy materials.展开更多
Rational design of bifunctional electrocatalysts for oxygen evolution reaction(OER)and hydrogen evolution reaction(HER)with excellent activity and stability is of great significance,since overall water splitting is a ...Rational design of bifunctional electrocatalysts for oxygen evolution reaction(OER)and hydrogen evolution reaction(HER)with excellent activity and stability is of great significance,since overall water splitting is a promising technology for sustainable conversion of clean energy.However,most electrocatalysts do not simultaneously possess optimal HER/OER activities and their electrical conductivities are intrinsically low,which limit the development of overall water splitting.In this paper,a strategy of electric field treatment is proposed and applied to Ni/Co_(3)O_(4) film to develop a novel bifunctional electrocatalyst.After treated by electric field,the conductive channels consisting of oxygen vacancies are formed in the Co_(3)O_(4) film,which remarkably reduces the resistance of the system by almost 2×10^(4) times.Meanwhile,the surface Ni metal electrode is partially oxidized to nickel oxide,which enhances the catalytic activity.The electric-field-treated Ni/Co_(3)O_(4) material exhibits super outstanding performance of HER,OER,and overall water splitting,and the catalytic activity is significantly superior to the state-of-the-art noble metal catalysts(Pt/C,RuO_(2),and RuO_(2)‖Pt/C couple).This work provides an effective and feasible method for the development of novel and efficient bifunctional electrocatalyst,which is also promising for wide use in the field of catalysis.展开更多
The coarsening behaviors of γ′ and γ″ phases in GH4169 alloy aged at 1023 and 1073 K with electric field treatment （EFT） were investigated by transmission electron microscopy （TEM） and positron annihilation li...The coarsening behaviors of γ′ and γ″ phases in GH4169 alloy aged at 1023 and 1073 K with electric field treatment （EFT） were investigated by transmission electron microscopy （TEM） and positron annihilation lifetime spectroscopy （PALS）. It is demonstrated that precipitation coarsening occurs, and the growth activation energies of γ′ and γ″phases can be decreased to 115.6 and 198.1 kJ.mo1-1, respectively, by applying the electric field. The formation of a large number of vacancies in the matrix is induced by EFT. Due to the occurrence of vacancy migration, the diffusion coefficients of A1 and Nb atoms are increased to be 1.6-5.0 times larger than those without EFT at 1023 or 1073 K. Furthermore, the formation of vacancy clusters is promoted by EFT, and the increase in strain energy for the coarsening of γ′ and γ″ phases can be counterbalanced by the formation of vacancy clusters.展开更多
Photocatalytic oxidation coupling of amines represents a green and cost-effective method for the synthesis of highly value-added imines under visible light irradiation.However,the catalytic efficiency was severely lim...Photocatalytic oxidation coupling of amines represents a green and cost-effective method for the synthesis of highly value-added imines under visible light irradiation.However,the catalytic efficiency was severely limited by poor visible light response and easy recombination of photogenerated charge carriers.Herein,we report a g-CgN_(4)/α-Bi_(2)O_(3)Z-scheme heterojunction via electrostatic self-assembly of g-C_(3)N_(4)nanosheets and oxygen-va-cancy-rich aα-Bi_(2)O_(3)microsphere for visible-light driven oxidative coupling of amines to imines in H_(2)0 as green solvent at room temperature.Amines with diverse functional groups were efficiently converted into the corre-sponding imines in good to excellent yields.Impressively,this photocatalytic protocol is applicable for the challenging hetero-coupling of two structurally different amines to construct complicated asymmetric imines,which is the first report of photocatalytic hetero-coupling of amines to imines to our knowledge.Furthermore,the Z-scheme heterojunction also demonstrated high stability and could be readily separated and reused without obvious decay in activity and selectivity.Comprehensive characterizations and control experiments reveal the construction of Z-scheme heterojunction with intimate interface between g-CgN4 and a-Bi_(2)O_(3)greatly boosts the transfer and separation of photogenerated charge carries and enhances the redox capability.Meanwhile,the surface oxygen vacancies in a-Biz_(2)O_(3)also benefits the separation of photogenerated charge carriers and acti-vation of reactants.These jointly contributed to an enhanced photocatalytic performance for oxidative coupling of amines to imines.展开更多
To further understand the effect of structural defects on the electrochemical and photocatalytic properties of TiO2, two synthetic approaches based on hydrothermal synthesis and post-synthetic chemical reduction to ac...To further understand the effect of structural defects on the electrochemical and photocatalytic properties of TiO2, two synthetic approaches based on hydrothermal synthesis and post-synthetic chemical reduction to achieve oxygen defect- implantation were developed herein. These approaches led to the formation of TiO2 nanorods with uniformly distributed defects in either the bulk or on the surface, or the combination of both, in the formed TiO2 nanorods （NRs）. Both approaches utilize unique TiN nanoparticles as the reaction precursor. Electron microscopy and Brunauer-Emmett-Teller （BET） analyses indicate that all the studied samples exhibit similar morphology and similar specific surface areas. X-ray photoelectron spectroscopy （XPS） and electron paramagnetic resonance （EPR） data confirm the existence of oxygen defects （Vo）. The photocatalytic properties of TiO2 with different types of implanted Vo were evaluated based on photocatalytic H2 production. By optimizing the concentration of Vo among the TiO2 NRs subjected to different treatments, significantly higher photocatalytic activities than that of the stoichiometric TiO2 NRs was achieved. The incident photon-to-current efficiency （IPCE） data indicate that the enhanced photocatalytic activity arises mainly from defect-assisted charge separation, which implies that photo-generated electrons or holes can be captured by Vo and suppress the charge recombination process. The results show that the defective TiO2 obtained by combining the two approaches exhibits the greatest photocatalytic activity enhancement amon~ all the samples.展开更多
With the advantage of fast charge transfer,heterojunction engineering is identified as a viable method to reinforce the anodes'sodium storage performance.Also,vacancies can effectively strengthen the Na+adsorption...With the advantage of fast charge transfer,heterojunction engineering is identified as a viable method to reinforce the anodes'sodium storage performance.Also,vacancies can effectively strengthen the Na+adsorption ability and provide extra active sites for Na+adsorption.However,their synchronous engineering is rarely reported.Herein,a hybrid of Co_(0.85)Se/WSe_(2) heterostructure with Se vacancies and N-doped carbon polyhedron(CoWSe/NCP)has been fabricated for the first time via a hydrothermal and subsequent selenization strategy.Spherical aberration-corrected transmission electron microscopy confirms the phase interface of the Co_(0.85)Se/WSe_(2) heterostructure and the existence of Se vacancies.Density functional theory simulations reveal the accelerated charge transfer and enhanced Na+adsorption ability,which are contributed by the Co_(0.85)Se/WSe_(2) heterostructure and Se vacancies,respectively.As expected,the CoWSe/NCP anode in sodium-ion battery achieves outstanding rate capability(339.6 mAh g^(−1) at 20 A g^(−1)),outperforming almost all Co/W-based selenides.展开更多
Rechargeable magnesium batteries(RMBs)have emerged as a promising next-generation electrochemical energy storage technology due to their superiority of low price and high safety.However,the practical applications of R...Rechargeable magnesium batteries(RMBs)have emerged as a promising next-generation electrochemical energy storage technology due to their superiority of low price and high safety.However,the practical applications of RMBs are severely limited by immature electrode materials.Especially,the high-rate cathode materials are highly desired.Herein,we propose a dualfunctional design of V_(2)O_(5)electrode with rational honeycomb-like structure and rich oxygen vacancies to enhance the kinetics synergistically.The result demonstrates that oxygen vacancies can not only boost the intrinsic electronic conductivity of V_(2)O_(5),but also enhance the Mg^(2+)diffusion kinetics inside the cathode,leading to the good high-rate performance.Moreover,ex-situ X-ray diffraction(XRD),transmission electron microscopy(TEM),and X-ray photoelectron spectroscopy(XPS)characterizations reveal that Mg^(2+)is mainly intercalated from the(101)plane of V_(2)O_(5)−X based on the insertion-type electrochemical mechanism;meanwhile,the highly reversible structure evolution during Mg^(2+)insertion/extraction is also verified.This work proposes that the dual-functional design of electrode has a great influence in enhancing the electrochemical performance of cathode materials for RMBs.展开更多
基金supported by the Department of Science and Technology,New Delhi,under SERB Scheme(SB/S1/PC-106/2012)
文摘In this work, the influence of trivalent rare-earth dopants（Sm and La） on the structure-activity properties of CeO2 was thoroughly studied for diesel soot oxidation. For this, an optimized 40% of Sm and La was incorporated into the CeO2 using a facile coprecipitation method from ultra-high dilute aqueous solutions. A systematic physicochemical characterization was carried out using X-ray diffraction（XRD）, transmission electron microscopy（TEM）, Brumauer-Emmett-teller method（BET） surface area, X-ray photoelectron spectroscopy（XPS）, Raman, and H2-temperature programmed reduction（TPR） techniques. The soot oxidation efficiency of the catalysts was investigated using a thermogravimetric method. The XRD results suggested the formation of nanocrystalline single phase CeO2-Sm2O3 and CeO2-La2O3 solid solutions. The Sm- and La-doped CeO2 materials exhibited smaller crystallite size and higher BET surface area compared with the pure CeO2. Owing to the difference in the oxidation states of the dopants（Sm3＋ and La3＋） and the Ce4＋, a number of oxygen vacancies were generated in CeO2-Sm2O3 and CeO2-La2O3 samples. The H2-TPR studies evidenced the improved reducible nature of the CeO2-Sm2O3 and CeO2-La2O3 samples compared with the CeO2. It was found that the addition of Sm and La to the CeO2 outstandingly enhanced its catalytic efficiency for the oxidation of diesel soot. The observed 50% soot conversion temperatures for the CeO2-Sm2O3, CeO2-La2O3 and CeO2 were ~790, 843 and 864 K（loose contact）, respectively, and similar activity order was also found under the tight contact condition. The high soot oxidation efficacy of the CeO2-Sm2O3 sample was attributed to numerous catalytically favourable properties, like smaller crystallite size, larger surface area, abundant oxygen vacancies, and superior reducible nature.
基金This work was financially supported by National Natural Science Foundation of China (Nos. 51808037, 21601136 and 21876010)the Science & Technology Development Fund of Tianjin Education Commission for Higher Education (No. 2018KJ126)the Fundamental Research Funds for the Central Universities (No. FRF-TP-16-060A1).
文摘Catalytic oxidation of toluene over noble metal catalysts is a representative reaction for elimination of volatile organic compounds(VOCs).However,to fully understand the activation of molecular oxygen and the role of active oxygen species generated in this reaction is still a challenging target.Herein,MgO nanosheets and single-atom Pt loaded MgO(Pt SA/MgO)nanosheets were synthesized and used as catalysts in toluene oxidation.The activation process of molecular oxygen and oxidation performance on the two catalysts were contrastively investigated.The Pt SA/MgO exhibited significantly enhanced catalytic activity compared to MgO.The oxygen vacancies can be easily generated on the Pt SA/MgO surface,which facilitate the activation of molecular oxygen and the formation of active oxygen species.Based on the experimental data and theoretical calculations,an active oxygen species promoted oxidation mechanism for toluene was proposed.In the presence of H2O,the molecular oxygen is more favorable to be dissociated to generate•OH on the oxygen vacancies of the Pt SA/MgO surface,which is the dominant active oxygen species.We anticipate that this work may shed light on further investigation of t10.1007/s12274-020-2765-1he oxidation mechanism of toluene and other VOCs over noble metal catalysts.
基金supported by the National Key R&D Plan(2016YFC02047)the National Natural Science Foundation of China(21822601,21777011,and 21501016)+2 种基金the Innovative Research Team of Chongqing(CXTDG201602014)the Key Natural Science Foundation of Chongqing(cstc2017jcyjBX0052)the Plan for ‘‘National Youth Talents” of the Organization Department of the Central Committee
文摘Aromatic ring-opening process is well recognized as the rate-determining step for catalytic toluene degradation. In photocatalytic toluene degradation, the toxic intermediates w让h harmful effects may be generated. To clarify the precise reaction mechanism and control the toxic intermediates generation, a closely combined in situ DRIFTS and DFT calculation is utilized to address these important issues. We construct the BiOCl w让h oxygen vacancies (OVs) and reveal the structure of OVs. The defect level caused by oxygen vacancies could promote the light adsorption and charge separation, which further boosts the activation of ring-opening species and enhances the generation process of free radicals. The reaction energy barriers of four possible ring-opening processes on defective BiOCl (OVBOC) are all declined in comparison with perfect BiOCl (BOC). The existence of oxygen vacancies could smooth the ratedetermining step so the ring-opening efficiency of photocatalytic toluene degradation is highly increased. Most importantly, the methyl species would be further oxidized and tend to open the benzene-ring at benzoic acid on BOC while the ring would be broken at the benzyl alcohol on OVBOC. These results indicate that the toluene degradation pathway is shortened via the surface OVs, which enables the production of radicals with high oxidation capability for the accelerated chain scission of the ring-opening intermediates. Finally, the efficiency of the key ring-opening process could be enormously improved and toxic intermediates are effectively restrained. The present work could provide new insights into the design of high-performance photocatalysts for efficient and safe degradation of VOCs in air.
基金supported by National Basic Research Program of China(2010CB732300)National Natural Science Foundation of China(21273110,20973091)Natural Science Foundation for the Youth(21203091)
文摘The CuO/CeO2 catalysts were investigated by means of X-ray diffraction （XRD）, laser Raman spectroscopy （LRS）, X-ray photoelectronic spectroscopy （XPS）, temperature-programmed reduction （TPR）, in situ Fourier transform infrared spectroscopy （FTIR） and NO＋CO reaction. The results revealed that the low temperature （〈150℃） catalytic performances were enhanced for CO pretreated samples. During CO pretreatment, the surface Cu＋/Cu0 and oxygen vacancies on ceria surface were present. The low va- lence copper species activated the adsorbed CO and surface oxygen vacancies facilitated the NO dissociation. These effects in turn led to higher activities of CuO/CeO2 for NO reduction. The current study provided helpful understandings of active sites and reaction mechanism in NO＋CO reaction.
基金support from the National Key R&D Program of China(2016YFA0202602 and2016YFA0202604)the National Natural Science Foundation of China(51701169 and 51871188)+2 种基金the Natural Science Foundation of Fujian Province(2017J05087)the Key Projects of Youth Natural Foundation for the Universities of Fujian Province of China(JZ160397)the“Double-First Class” Foundation of Materials and Intelligent Manufacturing Discipline of Xiamen University
文摘Lithium-rich layered oxides always suffer from low initial Coulombic efficiency,poor rate capability and rapid voltage fading.Herein,engineering oxygen vacancies in hierarchically Li1.2Mn0.54Ni0.13Co0.13O2 porous microspheres(L@S)is carried out to suppress the formation of irreversible Li20 during the initial discharge process and improve the Li+diffusion kinetics and structural stability of the cathode mateiral.As a result,the prepared L@S cathode delivers high initial Coulombic efficiency of 92.3%and large specific capacity of 292.6 mA h g^-1 at 0.1 C.More importantly,a large reversible capacity of 222 mA h g^-1 with a capacity retention of95.7%can be obtained after 100 cycles at 10 C.Even cycled at ultrahigh rate of 20 C,the L@S cathode can deliver stable reversible capacity of 153 mA h g^-1 after 100 cycles.Moreover,the full cell using L@S as cathode and Li4 Ti5 O12 as anode exhibits a relatively high reversible capacity of 141 mA h g^-1 with an outstanding voltage retention of 97%after 400 cycles at a large current density of 3 C.These results may shed light on the improvement of electrochemical performances of lithiumrich layered oxides via the multiscale coordinated design based on atomic defects,microstructure and composition.
基金supported by National Water Pollution Control and Treatment Science and Technology Major Project (No.2018ZX07110003)the National Natural Science Foundation of China (No.51779068)。
文摘Refractory organic pollutants in water threaten human health and environmental safety,and advanced oxidation processes (AOPs) are effective for the degradation of these pollutants.Catalysts play vital role in AOPs,and Ce-based catalysts have exhibited excellent performance.Recently,the development and application of Ce-based catalysts in various AOPs have been reported.Our study conducts the first review in this rapid growing field.This paper clarifies the variety and properties of Ce-based catalysts.Their applications in different AOP systems (catalytic ozonation,photodegradation,Fenton-like reactions,sulfate radicalbased AOPs,and catalytic sonochemistry) are discussed.Different Ce-based catalysts suit different reaction systems and produce different active radicals.Finally,future research directions of Ce-based catalysts in AOP systems are suggested.
基金supported by the Pilot Program of University of Liaoning Innovation and Education Reform~~
文摘Dielectric barrier discharge（DBD） plasma is considered to be a promising method to synthesize solid catalysts. In this work, DBD plasma was used to synthesize a nitrogen‐vacancy‐doped g‐C3N4 catalyst in situ for the first time. X‐ray diffraction, N2 adsorption, ultraviolet–visible spectroscopy, scanning electron microscopy, transmission electron microscopy, X‐ray photoelectron spectrosco‐py, electrochemical impedance spectroscopy, electron paramagnetic resonance, O2 tempera‐ture‐programmed desorption, and photoluminescence were used to characterize the obtained cat‐alysts. The photocatalytic H2O2 production ability of the as‐prepared catalyst was investigated. The results show that plasma treatment influences the morphology, structure, and optical properties of the as‐prepared catalyst. Nitrogen vacancies are active centers, which can adsorb reactant oxygen molecules, trap photoelectrons, and promote the transfer of photoelectrons from the catalyst to the adsorbed oxygen molecules for the subsequent reduction reaction. This work provides a new strat‐egy for synthesizing g‐C3N4‐based catalysts.
基金the FRC grant(UBD/RSCH/1.4/FICBF(b)/2022/046)received from Universiti Brunei Darussalam,Brunei Darussalam。
文摘Cerium oxide(CeO_(2)),one of the most significant rare-earth oxides,has attracted considerable interest over the past decades.This is primarily due to the ease in Ce^(3+)/Ce^(4+)redox ability as well as other factors that affect the efficacy of CeO_(2)and CeO_(2)-based materials.CeO_(2)and CeO_(2)-based materials have shown enhanced responses in catalytic and photocatalytic activities for environmental and biological applications.In addition,the formation of Ce^(3+)and oxygen vacancies in CeO_(2)has aided in enhancing CeO_(2)activities.In order to produce oxygen-deficient CeO_(2)and CeO_(2)-based materials,a variety of synthesis methods were used and are highlighted in this review.Therefore,this review compiles and discusses the mechanisms that involve oxygen vacancies,defects,and Ce^(3+)formation for environmental applications,such as photocatalytic dye degradation,photocatalytic CO_(2)reduction,and non-colored pollutants removal.The biological applications of CeO_(2),such as antioxidant enzyme mimetic,antioxidant reactive oxygen species/reactive nitrogen species,and antimicrobial activities,are also discussed.Additionally,future prospects are also suggested for future development and detailed investigations.
基金funded by the Higher Education Commission of Pakistan (HEC) IPFP (Grant No. PM-IPFP/HRD/ HEC/2011/3386) to Dr. Javed Iqbal Saggu and funding for HEC Ph.D. Scholar (Tariq Jan) under his supervision
文摘In this study, CeO2 nanostructures were synthesized by a soft chemical method. A hydrothermal treatment was observed to lead to an interesting morphological transformation of the nanoparticles into homogeneous microspheres composed of nanosheets with an average thickness of 40 nm. Structural analysis revealed the formation of a single-phase cubic fluorite structure of CeO2 for both samples. A Raman spectroscopic study confirmed the XRD results and furthermore indicated the presence of a large number of oxygen vacancies in the nanosheets. These oxygen vacancies led to room-temperature ferromagnetism （RTFM） of the CeO2 nanosheets with enhanced magnetic characteristics. Amazingly, the nanosheets exhibited substantially greater antibacterial activity than the nanoparticles. This greater antibacte- rial activity was attributed to greater exposure of high-surface-energy polar surfaces and to the presence of oxygen vacancies.
基金This study was supported by the National Basic Research of China(No.2015CB932500)the National Natural Science Foundations of China(Nos.51788104,51661135025 and 51522207)S.S.thanks financial support from Innovation Foundation for Science and Technology of Shenzhen(Nos.JCYJ20170307153548350 and JCYJ20170817172150505).
文摘Oxyge n vaca ncies impla ntation is an efficie nt way to adjust the physical and chemical properties of metal oxide nano materials to meet the requirements for particular applications.Through reasonable defects design,oxyge-deficient metal oxides with excellent optical and electrical properties are widely applied for environmental protection and energy uses.This review discusses recent advances in synthetic approaches of oxygervdeficient metal oxides and their applications in photocatalysis,electrocatalysis,and energy storage devices.The perspectives of oxyge n?deficie nt metal oxides for increased en ergy dema nd and en vironme ntal sustai liability are also exami ned.
基金This work was jointly supported by the National Natural Science Foundation of China(51972288 and 51672258)the Fundamental Research Funds for the Central Universities(2652018290).
文摘Reduction of CO2to solar fuels by artificial photosynthesis technology has attracted considerable attention. However, insufficient separation of charge carriers and weak CO2adsorption hamper the photocatalytic CO2 reduction activity. Herein, we tackle these challenges by introducing oxygen vacancies (OVs) on the two-dimensional Bi4Ti3O12ultrathin nanosheets via a combined hydrothermal and postreduction process. Selective photodeposition experiment of Pt over Bi4Ti3O12discloses that the ultrathin structure shortens the migration distance of photo-induced electrons from bulk to the surface, benefiting the fast participation in the CO2reduction reaction. The introduction of OVs on ultrathin Bi4Ti3O12 nanosheets leads to enormous amelioration on surface state and electronic structure, thereby resulting in enhanced CO2adsorption, photoabsorption and charge separation efficiency. The photocatalytic experiments uncover that ultrathin Bi4Ti3O12nanosheets with OVs reveal a largely enhanced CO2photoreduction activity for producing CO with a rate of 11.7 lmol g-1h-1in the gas–solid system, 3.2 times higher than that of bulk Bi4Ti3O12. This work not only yields efficient ultrathin photocatalysts with OVs, but also furthers our understanding on enhancing CO2reduction via cooperative tactics.
基金the support from the National Natural Science Foundation (No. 52171186)the Science and Technology Commission of Shanghai Municipality under No. 19511108100+1 种基金Shanghai Education Commission “Shuguang” scholar Project (16SG08)the financial support from the Center of Hydrogen Science, Shanghai Jiao Tong University
文摘MgH_(2) has attracted intensive interests as one of the most promising hydrogen storage materials.Nevertheless,the high desorption temperature,sluggish kinetics,and rapid capacity decay hamper its commercial application.Herein,2D TiO_(2) nanosheets with abundant oxygen vacancies are used to fabricate a flower-like MgH_(2)/TiO_(2) heterostructure with enhanced hydrogen storage performances.Particularly,the onset hydrogen desorption temperature of the MgH_(2)/TiO_(2) heterostructure is lowered down to 180℃(295℃ for blank MgH_(2)).The initial desorption rate of MgH_(2)/TiO_(2) reaches 2.116 wt% min^(-1) at 300℃,35 times of the blank MgH_(2) under the same conditions.Moreover,the capacity retention is as high as 98.5% after 100 cycles at 300℃,remarkably higher than those of the previously reported MgH_(2)-TiO_(2) composites.Both in situ HRTEM observations and ex situ XPS analyses confirm that the synergistic effects from multi-valance of Ti species,accelerated electron transportation caused by oxygen vacancies,formation of catalytic Mg-Ti oxides,and stabilized MgH_(2) NPs confined by TiO_(2) nanosheets contribute to the high stability and kinetically accelerated hydrogen storage performances of the composite.The strategy of using 2D substrates with abundant defects to support nano-sized energy storage materials to build heterostructure is therefore promising for the design of high-performance energy materials.
基金supported by the program B for Outstanding PhD candidate of Nanjing University.
文摘Rational design of bifunctional electrocatalysts for oxygen evolution reaction(OER)and hydrogen evolution reaction(HER)with excellent activity and stability is of great significance,since overall water splitting is a promising technology for sustainable conversion of clean energy.However,most electrocatalysts do not simultaneously possess optimal HER/OER activities and their electrical conductivities are intrinsically low,which limit the development of overall water splitting.In this paper,a strategy of electric field treatment is proposed and applied to Ni/Co_(3)O_(4) film to develop a novel bifunctional electrocatalyst.After treated by electric field,the conductive channels consisting of oxygen vacancies are formed in the Co_(3)O_(4) film,which remarkably reduces the resistance of the system by almost 2×10^(4) times.Meanwhile,the surface Ni metal electrode is partially oxidized to nickel oxide,which enhances the catalytic activity.The electric-field-treated Ni/Co_(3)O_(4) material exhibits super outstanding performance of HER,OER,and overall water splitting,and the catalytic activity is significantly superior to the state-of-the-art noble metal catalysts(Pt/C,RuO_(2),and RuO_(2)‖Pt/C couple).This work provides an effective and feasible method for the development of novel and efficient bifunctional electrocatalyst,which is also promising for wide use in the field of catalysis.
基金financially fnancially supported by the National Natural Science Foundation of China(No.51171039)the Major State Basic Research Development Program of China(No.2010CB631203)+1 种基金the Fundamental Research Funds for the Central Universities of China(No.N100602002)the 2010 Academy Awards Sponsorship of Doctoral Candidate for Newcomer of China(No.22002096)
文摘The coarsening behaviors of γ′ and γ″ phases in GH4169 alloy aged at 1023 and 1073 K with electric field treatment （EFT） were investigated by transmission electron microscopy （TEM） and positron annihilation lifetime spectroscopy （PALS）. It is demonstrated that precipitation coarsening occurs, and the growth activation energies of γ′ and γ″phases can be decreased to 115.6 and 198.1 kJ.mo1-1, respectively, by applying the electric field. The formation of a large number of vacancies in the matrix is induced by EFT. Due to the occurrence of vacancy migration, the diffusion coefficients of A1 and Nb atoms are increased to be 1.6-5.0 times larger than those without EFT at 1023 or 1073 K. Furthermore, the formation of vacancy clusters is promoted by EFT, and the increase in strain energy for the coarsening of γ′ and γ″ phases can be counterbalanced by the formation of vacancy clusters.
基金supported by the National Natural Science Foundation of China(No.22078350)the Natural Science Foundation of Shandong Province(ZR2020KB016)Shandong Energy Institute Fund(Grant no.SEII202138).
文摘Photocatalytic oxidation coupling of amines represents a green and cost-effective method for the synthesis of highly value-added imines under visible light irradiation.However,the catalytic efficiency was severely limited by poor visible light response and easy recombination of photogenerated charge carriers.Herein,we report a g-CgN_(4)/α-Bi_(2)O_(3)Z-scheme heterojunction via electrostatic self-assembly of g-C_(3)N_(4)nanosheets and oxygen-va-cancy-rich aα-Bi_(2)O_(3)microsphere for visible-light driven oxidative coupling of amines to imines in H_(2)0 as green solvent at room temperature.Amines with diverse functional groups were efficiently converted into the corre-sponding imines in good to excellent yields.Impressively,this photocatalytic protocol is applicable for the challenging hetero-coupling of two structurally different amines to construct complicated asymmetric imines,which is the first report of photocatalytic hetero-coupling of amines to imines to our knowledge.Furthermore,the Z-scheme heterojunction also demonstrated high stability and could be readily separated and reused without obvious decay in activity and selectivity.Comprehensive characterizations and control experiments reveal the construction of Z-scheme heterojunction with intimate interface between g-CgN4 and a-Bi_(2)O_(3)greatly boosts the transfer and separation of photogenerated charge carries and enhances the redox capability.Meanwhile,the surface oxygen vacancies in a-Biz_(2)O_(3)also benefits the separation of photogenerated charge carriers and acti-vation of reactants.These jointly contributed to an enhanced photocatalytic performance for oxidative coupling of amines to imines.
文摘To further understand the effect of structural defects on the electrochemical and photocatalytic properties of TiO2, two synthetic approaches based on hydrothermal synthesis and post-synthetic chemical reduction to achieve oxygen defect- implantation were developed herein. These approaches led to the formation of TiO2 nanorods with uniformly distributed defects in either the bulk or on the surface, or the combination of both, in the formed TiO2 nanorods （NRs）. Both approaches utilize unique TiN nanoparticles as the reaction precursor. Electron microscopy and Brunauer-Emmett-Teller （BET） analyses indicate that all the studied samples exhibit similar morphology and similar specific surface areas. X-ray photoelectron spectroscopy （XPS） and electron paramagnetic resonance （EPR） data confirm the existence of oxygen defects （Vo）. The photocatalytic properties of TiO2 with different types of implanted Vo were evaluated based on photocatalytic H2 production. By optimizing the concentration of Vo among the TiO2 NRs subjected to different treatments, significantly higher photocatalytic activities than that of the stoichiometric TiO2 NRs was achieved. The incident photon-to-current efficiency （IPCE） data indicate that the enhanced photocatalytic activity arises mainly from defect-assisted charge separation, which implies that photo-generated electrons or holes can be captured by Vo and suppress the charge recombination process. The results show that the defective TiO2 obtained by combining the two approaches exhibits the greatest photocatalytic activity enhancement amon~ all the samples.
基金support from the Natural Science Foundation of Jilin Province(Grant No.20200201073JC)the National Natural Science Foundation of China(Grant No.52130101)+1 种基金Interdisciplinary Integration and Innovation Project of JLU(Grant No.JLUXKJC2021ZY01)the Fundamental Research Funds for the Central Universities.
文摘With the advantage of fast charge transfer,heterojunction engineering is identified as a viable method to reinforce the anodes'sodium storage performance.Also,vacancies can effectively strengthen the Na+adsorption ability and provide extra active sites for Na+adsorption.However,their synchronous engineering is rarely reported.Herein,a hybrid of Co_(0.85)Se/WSe_(2) heterostructure with Se vacancies and N-doped carbon polyhedron(CoWSe/NCP)has been fabricated for the first time via a hydrothermal and subsequent selenization strategy.Spherical aberration-corrected transmission electron microscopy confirms the phase interface of the Co_(0.85)Se/WSe_(2) heterostructure and the existence of Se vacancies.Density functional theory simulations reveal the accelerated charge transfer and enhanced Na+adsorption ability,which are contributed by the Co_(0.85)Se/WSe_(2) heterostructure and Se vacancies,respectively.As expected,the CoWSe/NCP anode in sodium-ion battery achieves outstanding rate capability(339.6 mAh g^(−1) at 20 A g^(−1)),outperforming almost all Co/W-based selenides.
基金the National Natural Science Foundation of China(Nos.21875198,22005257,and 22021001)Natural Science Foundation of Fujian Province of China(No.2020J05009)for financial support.
文摘Rechargeable magnesium batteries(RMBs)have emerged as a promising next-generation electrochemical energy storage technology due to their superiority of low price and high safety.However,the practical applications of RMBs are severely limited by immature electrode materials.Especially,the high-rate cathode materials are highly desired.Herein,we propose a dualfunctional design of V_(2)O_(5)electrode with rational honeycomb-like structure and rich oxygen vacancies to enhance the kinetics synergistically.The result demonstrates that oxygen vacancies can not only boost the intrinsic electronic conductivity of V_(2)O_(5),but also enhance the Mg^(2+)diffusion kinetics inside the cathode,leading to the good high-rate performance.Moreover,ex-situ X-ray diffraction(XRD),transmission electron microscopy(TEM),and X-ray photoelectron spectroscopy(XPS)characterizations reveal that Mg^(2+)is mainly intercalated from the(101)plane of V_(2)O_(5)−X based on the insertion-type electrochemical mechanism;meanwhile,the highly reversible structure evolution during Mg^(2+)insertion/extraction is also verified.This work proposes that the dual-functional design of electrode has a great influence in enhancing the electrochemical performance of cathode materials for RMBs.
