Novel graphene-like boron nitride(BN)/Bi_(3)O_(4)Br photocatalysts have been controllably synthesized through a facile solvothermal method for the first time. Layer contact stacking between graphene-like BN and ultrat...Novel graphene-like boron nitride(BN)/Bi_(3)O_(4)Br photocatalysts have been controllably synthesized through a facile solvothermal method for the first time. Layer contact stacking between graphene-like BN and ultrathin Bi_(3)O_(4)Br was achieved with strong interaction. Dehalogenation is designed to harvest more visible light, and the ultrathin structure of Bi_(3)O_(4)Br is designed to accelerate charge transfer from inside to the surface. After graphene-like BN was engineered, photocatalytic performance greatly improved under visible light irradiation. Graphene-like BN can act as a surface electron-withdrawing center and adsorption center, facilitating molecular oxygen activation. O_(2)^(·-)was determined to be the main active species during the degradation process through analyses of electron spin resonance and XPS valence band spectra.展开更多
Tuning the coordination environment is the research axis of single atom catalysts (SACs). SACs are commonly stabilized by various defects from support. Here, we report a lattice confined Pd SAC using MnO_(2) as suppor...Tuning the coordination environment is the research axis of single atom catalysts (SACs). SACs are commonly stabilized by various defects from support. Here, we report a lattice confined Pd SAC using MnO_(2) as support. Compared with the Pd clusters anchored on the surface, the lattice confined Pd single atoms allows spontaneous exaction of surrounding lattice oxygen at room temperature when employed in CO oxidation. The MnO_(2) supported Pd SAC exhibited a high turnover frequency of 0.203 s^(−1) at low reaction temperature, which is higher than that of recently reported Pd SACs. Theoretical calculations also confirmed the confined monatomic Pd activate lattice oxygen with an ultralow energy barrier. Our results illustrate that the unique coordination environment of single atom provided by lattice confinement is promising to boost the activity of SACs.展开更多
Piezoelectric semiconductors bear the bifunctional photocatalysis and piezocatalysis,while the absent or weak internal charge driving force severely restricts its catalytic activity.Developing polarization strategy is...Piezoelectric semiconductors bear the bifunctional photocatalysis and piezocatalysis,while the absent or weak internal charge driving force severely restricts its catalytic activity.Developing polarization strategy is desirable,and particularly understanding its mechanism from a microscopic perspective remains scanty.Herein,we report a secondary recrystallization approach to achieving the simultaneous micro-and macroscopic polarization enhancement on Bi2WO6 nanosheets for boosting piezo-photocatalytic oxygen activation,and unravel the mechanism at an atom-level.The secondary recrystallization process not only results in a strengthened distortion of[WO6]octahedra with distortion index enhancement by~20%for a single octahedron,but also enables lateral crystal growth of nanosheets along the ab plane(av.50 to 180 nm),which separately allows the rise in dipole moment of unit cell(e.g.,1.63 D increase along a axis)and the stacking of the distorted[WO6]octahedron to accumulate the unit cell dipole,collectively contributing to the considerably strengthened spontaneous polarization and piezoelectricity.Besides,exposure of large-area{001}front facet enables more efficient capture and conversion of stress into piezo-potential.Therefore,the well-recrystallized Bi2WO6 nanosheets exhibit considerably promoted piezo-photocatalytic reactive oxygen species generation,given the decreased specific surface area.This work presents a feasible methodology to regulate inside-out polarization for guiding carriers transfer behavior,and may advance the solid understanding on the intrinsic mechanism.展开更多
Using a ditopic organic linker 4-(1H-pyrazol-4-yl)benzoic acid(H_(2)pba),FICN-6,a metal-organic framework containing both Cu_(2)(O_(2)CR)_(4)and Cu_(3)(OH)(pyz)_(3)(O_(2)CR)secondary building units(SBUs),was synthesiz...Using a ditopic organic linker 4-(1H-pyrazol-4-yl)benzoic acid(H_(2)pba),FICN-6,a metal-organic framework containing both Cu_(2)(O_(2)CR)_(4)and Cu_(3)(OH)(pyz)_(3)(O_(2)CR)secondary building units(SBUs),was synthesized.FICN-6 adopts in an unusual intercatenated structure with SBUs from two distinct networks connecting to each other.Presence of Cu_(3)clusters makes FICN-6 a good heterogeneous catalyst for oxygen activation and aerobic oxidative C-C coupling of organic boronic acids.展开更多
Largely limited by the high dissociation energy of the O—O bond,the photocatalytic molecular oxygen activation is highly challenged,which re strains the application of photocatalytic oxidation technology for atmosphe...Largely limited by the high dissociation energy of the O—O bond,the photocatalytic molecular oxygen activation is highly challenged,which re strains the application of photocatalytic oxidation technology for atmospheric pollutants removal.Herein,we design and fabricate the InP QDs/g-C_(3)N_(4) compounds.The introduction of InP QDs promotes the charge transfer within the interface resulting in the effective separation of photo-generated carriers.Furthermore,InP QDs greatly facilitates the activation of molecular oxygen and promote the formation of O_(2)·under visible-light illuminatio n.These conclusions are identified by experimental and calculation results.Hence,NO can be combined with the O_(2)·to form O—O—N—O intermediate to direct conversion into NO_(3).As a result,the NO removal ratio of g-C_(3)N_(4) has a one fold increase after InP QDs loaded and the generation of NO_(2) is effectively inhibited.This wo rk may provide a strategy to design highly efficient materials for molecular oxygen activation.展开更多
Sunlight-driven activation of molecular oxygen(O_(2))for organic oxidation reactions offers an appealing strategy to cut down the reliance on fossil fuels in chemical industry,yet it remains a great challenge to simul...Sunlight-driven activation of molecular oxygen(O_(2))for organic oxidation reactions offers an appealing strategy to cut down the reliance on fossil fuels in chemical industry,yet it remains a great challenge to simultaneously tailor the charge kinetics and promote reactant chemisorption on semiconductor catalysts for enhanced photocatalytic performance.Herein,we report iron sites immobilized on defective BiOBr nanosheets as an efficient and selective photocatalyst for activation of O_(2) to singlet oxygen(^(1)O_(2)).These Fe^(3+) species anchored by oxygen vacancies can not only facilitate the separation and migration of photogenerated charge carrier,but also serve as active sites for effective adsorption of 02.Moreover,low-temperature phosphorescence spectra combined with X-ray photoelectron spectroscopy(XPS)and electronic paramagnetic resonance(EPR)spectra under illumination reveal that the Fe species can boost the quantum yield of excited triplet state and accelerate the energy transfer from excited triplet state to adsorbed O2 via a chemical loop of Fe^(3+)/Fe^(2+),thereby achieving highly efficient and selective generation of ^(1)O_(2).As a result,the versatile iron sites on defective BiOBr nanosheets contributes to near-unity conversion rate and selectivity in both aerobic oxidative coupling of amines to imines and sulfoxidation of organic sulfides.This work highlights the significant role of metal sites anchored on semiconductors in regulating the charge/energy transfer during the heterogeneous photocatalytic process,and provides a new angle for designing high-performance photocatalysts.展开更多
In recent decade, Au nanoclusters of atomic precision (AunLm, where L= organic ligand: thiolate andphosphine) have been shown as a new promising nanogold catalyst. The well-defined AunLm catalystspossess unique ele...In recent decade, Au nanoclusters of atomic precision (AunLm, where L= organic ligand: thiolate andphosphine) have been shown as a new promising nanogold catalyst. The well-defined AunLm catalystspossess unique electronic properties and frameworks, providing an excellent opportunity to correlate theintrinsic catalytic behavior with the cluster's framework as well as to study the catalytic mechanismsover gold nanoclusters. In this review, we only demonstrate the important roles of the gold nanoclustersin the oxygen activation (e.g., 302 to 102) and their selective oxidations in the presence of oxygen (e.g., COto C02, sulfides to sulfoxides, alcohol to aldehyde, styrene to styrene epoxide, amines to imines, andglucose to gluconic acid). The size-specificity (Au25 (1.3 nm), Au38 (].5 nm), Au144 (1.9 nm), etc.), ligandengineering (e.g., aromatic vs aliphatic), and doping effects (e.g., copper, silver, palladium, and platinum)are discussed in details. Finally, the proposed reactions' mechanism and the relationships of clusters'structure and activity at the atomic level also are presented.展开更多
Cobalt-rich perovskite oxides play a paramount role in catalyzing oxygen evolution reaction(OER)on account of their acceptable intrinsic activity but are still challenging due to the high costs and undesired stability...Cobalt-rich perovskite oxides play a paramount role in catalyzing oxygen evolution reaction(OER)on account of their acceptable intrinsic activity but are still challenging due to the high costs and undesired stability.In response to the defects,herein,the Mg-incorporated perovskite cobaltite SrCo_(0.6)Fe_(0.3M)g_(0.1)O_(3-δ)(SCFM-0.1)is proposed as a novel earth-abundant and durable OER electrocatalyst.A well-consolidated cubic-symmetry structure and more active oxygen intermediates are enabled upon Mg substitution.Hence,the optimized SCFM-0.1 perovskite oxide achieves prominent OER electrocatalytic performance,that is,a low overpotential of only 320 mV at 10 mA cm^(-2),a small Tafel slope of 65 mV dec^(-1),as well as an outstanding durability within 20 h,substantially outperforming that of the pristine SrCo_(0.7)Fe_(0.3)O_(3-δ)and benchmark Ba_(0.5)Sr_(0.5)Co_(0.8)Fe_(0.2)O_(3-δ)and IrO_(2) catalysts.The strong pHdependent behavior associated with lattice oxygen activation mechanism for SCFM-0.1 catalyst is also confirmed.This work paves a unique avenue to develop cost-effective and robust perovskite cobaltites for efficient OER electrocatalysis.展开更多
<img src="Edit_bdc7d851-e537-40df-990c-d678defa9648.png" alt="" />(M = Au, Ag, Cu;<span lang="EN-US" style="font-size:9pt;font-family:"color:black;"><i>n&...<img src="Edit_bdc7d851-e537-40df-990c-d678defa9648.png" alt="" />(M = Au, Ag, Cu;<span lang="EN-US" style="font-size:9pt;font-family:"color:black;"><i>n</i></span>= 1, 2, 3) clusters were used as a cluster model to study the activation of oxygen molecules on single-atom catalysts. Structures of <img src="Edit_bb84deb7-e24a-4777-a2f6-a1621ddd2afc.png" alt="" /> clusters were studied by density functional calculations with global optimization. For each <span style="font-family:"color:black;white-space:normal;"><i>n</i></span>, the most stable structures are quite similar for different metal types, and the oxygen molecule prefers to be adsorbed onto M atoms. It is found that the activation degree of oxygen is higher on clusters with non-noble metal Cu than that of Ag or Au containing clusters, by comparing the changes of O-O bond length and vibrational frequency, natural charge population analysis, Fuzzy bond order analysis, and energy barriers of O<sub>2</sub> dissociation. CO oxidation was used as a probe reaction to study the reactivity of Cu-containing clusters, and it is found that the reactivity decreases with the increase of the size of silicon-oxygen clusters. Our results give a new aspect to understand the reaction mechanism of non-precious metal single-atom catalyst for oxygen activation with high efficiency.展开更多
Metal-based perovskite oxides have contributed significantly to the advanced oxidation processes(AOPs)due to their diverse active sites and excellent compositional/structural flexibility.In this study,we specially des...Metal-based perovskite oxides have contributed significantly to the advanced oxidation processes(AOPs)due to their diverse active sites and excellent compositional/structural flexibility.In this study,we specially designed a perovskite oxide with abundant oxygen vacancies,SrCo_(0.8)Fe_(0.2)O_(3)(SCF),and firstly applied it as a catalyst in peroxymonosulfate(PMS) activation towards organic pollutants degradation.The result revealed that the prepared SCF catalyst exhibited excellent performance on organic compounds degradation.Besides,SCF showed much better activity than La_(0.5)Sr_(0.5)Co_(0.8)Fe_(0.2)O_(3)(LSCF) in terms of reaction rate and stability for the degradation of the organic compounds.Based on the analysis of scanning electron microscope,transmission electron microscope,X-ray diffraction,N_(2) adsorption-desorption,X-ray photoelectron spectroscopy and electron paramagnetic resonance,it was confirmed that the perovskite catalysts with high content of Sr doping at A-site could effectively create a defect-rich surface and optimize its physicochemical properties,which was responsible for the excellent heterogeneous catalytic activity of SCF.SCF can generate three highly active species:~1 O_(2),SO_(4)^(-)· and ·OH in PMS activation,revealing the degradation process of organic compounds was a coupled multiple active species in both radical and nonradical pathway.Moreover,it was mainly in a radical pathway in the degradation through PMS activation on SCF and SO_(4)^(-)· radicals produced were the dominant species in SCF/PMS system.This study demonstrated that perovskite-type catalysts could enrich OVs efficiently by doping strategy and regulate the PMS activation towards sulfate radical-based AOPs.展开更多
The function-led design of porous hydrochar from mineral-rich biowaste for environmental applications inevitably suffers from carbon-ash recalcitrance.However,a method to alter the original carbon skeleton with ash re...The function-led design of porous hydrochar from mineral-rich biowaste for environmental applications inevitably suffers from carbon-ash recalcitrance.However,a method to alter the original carbon skeleton with ash remains elusive and hinders the availability of hydrochar.Herein,we propose a facile strategy for breaking the rigid structure of carbon-ash coupled hydrochar using phase-tunable molten carbonates.A case system was designed in which livestock manure and NaHCO3 were used to prepare the activated hydrochar,and NH3 served as the target contaminant.Due to the redox effect,we found that organic fractions significantly advanced the melting temperature of Na2CO3 below 800℃.The Na species steadily broke the carbon-ash interaction as the thermal intensity increased and transformed inorganic constituents to facilitate ash dissolution,rebuilding the hydrochar skeleton with abundant hierarchical channels and active defect edges.The surface polarity and mesopore distribution collectively governed the five cycles NH3 adsorption attenuation process.Manure hydrochar delivered favorable potential for application with a maximum overall adsorption capacity of 100.49 mg·g^(-1).Integrated spectroscopic characterization and theoretical computations revealed that incorporating NH3 on the carbon surface could transfer electrons to chemisorbed oxygen,which promoted the oxidation of pyridine-N during adsorption.This work offers deep insight into the structure function correlation of hydrochar and inspires a more rational design of engineered hydrochar from high-ash biowaste.展开更多
Peach fruits [Prumus persica (L.) Batsch, cv. Yuhuasanhao] were used as materials to investigate the changes of reactive oxygen species (ROS) and related enzymes in mitochondria respiration during storage and then...Peach fruits [Prumus persica (L.) Batsch, cv. Yuhuasanhao] were used as materials to investigate the changes of reactive oxygen species (ROS) and related enzymes in mitochondria respiration during storage and then their influence on senescence of harvested Peach fruits was studied. The results showed that low temperature (5℃) strongly inhibited the reduction of firmness and the increase in respiration rate. During storage at ambient temperature (20℃), ROS had a cumulative process while malondialdehye (MDA) content continued to increase in associated with enhanced membrane lipid peroxidation. Lipoxygenase (LOX) activity was strongly inhibited under the low temperature condition. The activities of succinic dehydrogenase (SDH), cytochrome C oxidase (CCO), and Ca^2+-ATPase declined to a certain extent at ambient temperature, while they showed higher activities at low temperature, which may be related to lower membrane lipid peroxidation at low temperature. Higher Ca^2+ content at ambient temperature may be responsible for impairment of mitochondrial function, thus, leading to fruit senescence. The results showed that under low temperature condition, the low accumulation of ROS and the low level of membrane lipid peroxidation could maintain the function of mitochondria that would help to delay the senescence of peach fruits. These suggested a close relationship existed between ROS metabolism and mitochondrial respiration. It can be inferred that the low temperature helps to delay senescence of peach fruits via suppression of ROS and related enzymes, maintain better homeostasis of Ca^2+ in mitochondria and thus better mitochondrial functions.展开更多
The changes in content of Ca2 + and CaM, Ca2 + -ATPase activity and active oxygen metabolism during strawberry (Fragaria ananassa Duch. cv. Chunxing) fruits maturation and senescence were investigated in this study. T...The changes in content of Ca2 + and CaM, Ca2 + -ATPase activity and active oxygen metabolism during strawberry (Fragaria ananassa Duch. cv. Chunxing) fruits maturation and senescence were investigated in this study. The results showed that the soluble Ca2+ content and SOD activity in fruits tended to decline and O2 production rate to increase, the Ca2 + -ATPase activity peaked at first and then declined during fruits maturation and senescence. There were the highest CaM content at white stage in preharvest fruits and at marked senescence stage in postharvest ones. The above biochemical changes in fruits stored at low temperature (4℃)were slower than those stored at normal temperature(25℃). Thus, it indicated that the stimulation of calcium messenger system and accumulation of active oxygen free radical were closely related to fruits maturation and senescence.展开更多
La_(2)O_(3) catalyzed oxidative coupling of methane(OCM) is a promising process that converts methane directly to valuable C_(2)(ethylene and ethane) products. Our online MS transient study results indicate that prist...La_(2)O_(3) catalyzed oxidative coupling of methane(OCM) is a promising process that converts methane directly to valuable C_(2)(ethylene and ethane) products. Our online MS transient study results indicate that pristine surface without carbonate species demonstrates a higher selectivity to C_(2) products, and a lower light-off temperature as well. Further study is focused on carbonate-free La_(2)O_(3) catalyst surface for identification of active oxygen species associated with such products behavior. XPS reveals unique oxygen species with O 1 s binding energy of 531.5 e V correlated with OCM catalytic activity and carbonates removal. However, indicated thermal stability of this species is much higher than the surface peroxide or superoxide structures proposed by earlier computation models. Motivated by experimental results,DFT calculations reveal a new more stable peroxide structure, formed at the subsurface hexacoordinate lattice oxygen sites, with energy 2.18 e V lower than the previous models. The new model of subsurface peroxide provides a perspective for understanding of methyl radicals formation and C_(2) products selectivity in OCM over La_(2)O_(3) catalyst.展开更多
Under artificially-simulated complex salt-alkali stress, the levels of active oxygen metabolism in roots were studied using three-year-old cutting seedlings of Spiraea × bumalda ‘Gold Mound' and Spiraea × ...Under artificially-simulated complex salt-alkali stress, the levels of active oxygen metabolism in roots were studied using three-year-old cutting seedlings of Spiraea × bumalda ‘Gold Mound' and Spiraea × bumalda ‘Gold Flame'. The present study aimed at exploring the antioxidant capacity in roots of spiraeas and revealing their adaptability to salt-alkali stress. Results indicate that the oxygen free radicals contents, electrolyte leakage rates and MDA contents in roots of Spiraea × bumalda 'Gold Mound' and Spiraea × bumalda 'Gold Flame' show an increasing tendency with the increases of the salinity and pH value, whereas the activities of superoxide dismutase (SOD), peroxidase (POD) and catalase (CAT) all increased firstly and then decreased. With the increase in intensity of salt-alkali stress, the CAT activity in roots of Spiraea × bumalda ‘Gold Flame' is higher and the increasing extents in the oxygen free radicals contents, electrolyte leakage rates as well as MDA contents are lower compared with Spiraea × bumalda ‘Gold Mound', indicating that Spiraea × bumalda ‘Gold Flame' has a stronger antioxidant capacity.展开更多
The effect of oxygen partial pressure (Po2) during the channel layer deposition on bias stability of amorphous indium-gallium-zinc oxide (a-IGZO) thin film transistors (TFTs) is investigated. As Po2 increases fr...The effect of oxygen partial pressure (Po2) during the channel layer deposition on bias stability of amorphous indium-gallium-zinc oxide (a-IGZO) thin film transistors (TFTs) is investigated. As Po2 increases from 10% to 30%, it is found that the device shows enhanced bias stress stability with significantly reduced threshold voltage drift under positive gate bias stress. Based on the x-ray photoelectron spectroscopy measurement, the concentration of oxygen vacancies (Or) within the a-IGZO layer is suppressed by increasing Po2. Meanwhile, the low-frequency noise analysis indicates that the average trap density near the channel/dielectric interface continuously drops with increasing Po2. Therefore, the improved interface quality with increasing Po2 during the channel layer deposition can be attributed to the reduction of interface Ov-related defects, which agrees with the enhanced bias stress stability of the a-IGZO TFTs.展开更多
Oxygen transfer presents a serious challenge in the application of liquid lead as a nuclear coolant in advanced reactors. To mitigate corrosion by liquid lead in contact with steel, carefully controlling the oxygen co...Oxygen transfer presents a serious challenge in the application of liquid lead as a nuclear coolant in advanced reactors. To mitigate corrosion by liquid lead in contact with steel, carefully controlling the oxygen concentration has been used as an effective way. Oxygen needs to mix in liquid lead uniformly and quickly. To enhance oxygen transport in liquid lead, nanoparticles are added to the liquid metal. In the current study, a lattice Boltzmann method is applied to investigate natural convection of copper/lead and aluminum oxide/lead in two-dimensional simplified container. Two thermal boundary cases are evaluated in order to check the effect of different natural convection flow patterns on oxygen transport. Some useful information are obtained such as improvement in natural convection and reduction in oxygen equilibrium time.展开更多
The introduction of nitrogen heteroatoms into carbon materials is a facile and efficient strategy to regulate their reactivities and facilitate their potential applications in energy conversion and storage. However,mo...The introduction of nitrogen heteroatoms into carbon materials is a facile and efficient strategy to regulate their reactivities and facilitate their potential applications in energy conversion and storage. However,most of nitrogen heteroatoms are doped into the bulk phase of carbon without site selectivity, which significantly reduces the contacts of feedstocks with the active dopants in a conductive scaffold. Herein we proposed the chemical vapor deposition of a nitrogen-doped graphene skin on the 3D porous graphene framework and donated the carbon/carbon composite as surface N-doped grapheme(SNG). In contrast with routine N-doped graphene framework(NGF) with bulk distribution of N heteroatoms, the SNG renders a high surface N content of 1.81 at%, enhanced electrical conductivity of 31 S cm^(-1), a large surface area of 1531 m^2 g^(-1), a low defect density with a low I_D/I_G ratio of 1.55 calculated from Raman spectrum, and a high oxidation peak of 532.7 ℃ in oxygen atmosphere. The selective distribution of N heteroatoms on the surface of SNG affords the effective exposure of active sites at the interfaces of the electrode/electrolyte, so that more N heteroatoms are able to contact with oxygen feedstocks in oxygen reduction reaction or serve as polysulfide anchoring sites to retard the shuttle of polysulfides in a lithium–sulfur battery. This work opens a fresh viewpoint on the manipulation of active site distribution in a conductive scaffolds for multi-electron redox reaction based energy conversion and storage.展开更多
The article uses the method of regression statistics to obtain the regression formula of iron fluid nodule ratio Q and compacted graphite ratio R, through rare earth magnesium treatment. At the same time it has given ...The article uses the method of regression statistics to obtain the regression formula of iron fluid nodule ratio Q and compacted graphite ratio R, through rare earth magnesium treatment. At the same time it has given thejudging figure of Q and R, considering oxygen activity and temperature. When using oxygen activity to judgenodule ratio and compacted graphite ratio of the ironfluid treated by rare earth magnesium alloy, its limit value changes with the change of temperature.展开更多
基金financially supported by the Fundamental Research Funds for the Central Universities (No.30922010302)the Start-Up Grant from Nanjing University of Science and Technology (AE89991/397)。
文摘Novel graphene-like boron nitride(BN)/Bi_(3)O_(4)Br photocatalysts have been controllably synthesized through a facile solvothermal method for the first time. Layer contact stacking between graphene-like BN and ultrathin Bi_(3)O_(4)Br was achieved with strong interaction. Dehalogenation is designed to harvest more visible light, and the ultrathin structure of Bi_(3)O_(4)Br is designed to accelerate charge transfer from inside to the surface. After graphene-like BN was engineered, photocatalytic performance greatly improved under visible light irradiation. Graphene-like BN can act as a surface electron-withdrawing center and adsorption center, facilitating molecular oxygen activation. O_(2)^(·-)was determined to be the main active species during the degradation process through analyses of electron spin resonance and XPS valence band spectra.
基金X.Liao gratefully thanks the support from the National Natural Science Foundation of China(No.21706216)the Sichuan Science and Technology Program(2020YFG0162)+3 种基金the Young Scholar Project in Xihua University.X.Li acknowledges the support from the National Natural Science Foundation of China(No.21972163)the Fundamental Research Funds for the Central Universities and DHU Distinguished Young Professor Program,and the Development Fund for Shanghai Talents.Z.Jiang acknowledges financial support from the Joint Fund U1732267.M.Y.thanks the JSPS KAKENHI(No.JP 18H05517)JST-CREST for financial supports,and Riken SPring-8 for the approval of the SRXRD measurement(20190028)EXAFS studies were carried out at the BL14W1 beamline in the Shanghai Synchrotron Radiation Facility[63],Shanghai Institute of Applied Physics,China(16ssr-f00787).X.Liao gratefully thanks the useful discussion with Ya Wang and Yanmin Liu.
文摘Tuning the coordination environment is the research axis of single atom catalysts (SACs). SACs are commonly stabilized by various defects from support. Here, we report a lattice confined Pd SAC using MnO_(2) as support. Compared with the Pd clusters anchored on the surface, the lattice confined Pd single atoms allows spontaneous exaction of surrounding lattice oxygen at room temperature when employed in CO oxidation. The MnO_(2) supported Pd SAC exhibited a high turnover frequency of 0.203 s^(−1) at low reaction temperature, which is higher than that of recently reported Pd SACs. Theoretical calculations also confirmed the confined monatomic Pd activate lattice oxygen with an ultralow energy barrier. Our results illustrate that the unique coordination environment of single atom provided by lattice confinement is promising to boost the activity of SACs.
基金the National Key Research and Development Program of China(No.2022YFB3803600)the National Natural Science Foundation of China(Nos.52272244 and 51972288)+1 种基金the Fundamental Research Funds for the Central Universities(No.2652022202)2021 Graduate Innovation Fund Project of China University of Geosciences,Beijing(No.ZY2021YC006).
文摘Piezoelectric semiconductors bear the bifunctional photocatalysis and piezocatalysis,while the absent or weak internal charge driving force severely restricts its catalytic activity.Developing polarization strategy is desirable,and particularly understanding its mechanism from a microscopic perspective remains scanty.Herein,we report a secondary recrystallization approach to achieving the simultaneous micro-and macroscopic polarization enhancement on Bi2WO6 nanosheets for boosting piezo-photocatalytic oxygen activation,and unravel the mechanism at an atom-level.The secondary recrystallization process not only results in a strengthened distortion of[WO6]octahedra with distortion index enhancement by~20%for a single octahedron,but also enables lateral crystal growth of nanosheets along the ab plane(av.50 to 180 nm),which separately allows the rise in dipole moment of unit cell(e.g.,1.63 D increase along a axis)and the stacking of the distorted[WO6]octahedron to accumulate the unit cell dipole,collectively contributing to the considerably strengthened spontaneous polarization and piezoelectricity.Besides,exposure of large-area{001}front facet enables more efficient capture and conversion of stress into piezo-potential.Therefore,the well-recrystallized Bi2WO6 nanosheets exhibit considerably promoted piezo-photocatalytic reactive oxygen species generation,given the decreased specific surface area.This work presents a feasible methodology to regulate inside-out polarization for guiding carriers transfer behavior,and may advance the solid understanding on the intrinsic mechanism.
基金the National Natural Science Foundation of China(No.22005306)for financial support。
文摘Using a ditopic organic linker 4-(1H-pyrazol-4-yl)benzoic acid(H_(2)pba),FICN-6,a metal-organic framework containing both Cu_(2)(O_(2)CR)_(4)and Cu_(3)(OH)(pyz)_(3)(O_(2)CR)secondary building units(SBUs),was synthesized.FICN-6 adopts in an unusual intercatenated structure with SBUs from two distinct networks connecting to each other.Presence of Cu_(3)clusters makes FICN-6 a good heterogeneous catalyst for oxygen activation and aerobic oxidative C-C coupling of organic boronic acids.
基金the National Natural Science Foundation of China(No.U1862111)Sichuan Science andTechnology Program(No.2020ZDZX0008)+3 种基金Sichuan Provincial International Cooperation Project(No.2019YFH0164)International Collaboration Project of Chengdu City(No.2017-GH02-00014HZ)Graduate Scientific Research Innovation Foundation of SWPU(No.2019cxyb013)Cheung Kong Scholars Programme of China。
文摘Largely limited by the high dissociation energy of the O—O bond,the photocatalytic molecular oxygen activation is highly challenged,which re strains the application of photocatalytic oxidation technology for atmospheric pollutants removal.Herein,we design and fabricate the InP QDs/g-C_(3)N_(4) compounds.The introduction of InP QDs promotes the charge transfer within the interface resulting in the effective separation of photo-generated carriers.Furthermore,InP QDs greatly facilitates the activation of molecular oxygen and promote the formation of O_(2)·under visible-light illuminatio n.These conclusions are identified by experimental and calculation results.Hence,NO can be combined with the O_(2)·to form O—O—N—O intermediate to direct conversion into NO_(3).As a result,the NO removal ratio of g-C_(3)N_(4) has a one fold increase after InP QDs loaded and the generation of NO_(2) is effectively inhibited.This wo rk may provide a strategy to design highly efficient materials for molecular oxygen activation.
基金supported by the National Key R&D Program of China(No.2017YFA0700104)the National Natural Science Foundation of China(Nos.21905204,21931007,and 21790052)111 Project of China(No.D17003).
文摘Sunlight-driven activation of molecular oxygen(O_(2))for organic oxidation reactions offers an appealing strategy to cut down the reliance on fossil fuels in chemical industry,yet it remains a great challenge to simultaneously tailor the charge kinetics and promote reactant chemisorption on semiconductor catalysts for enhanced photocatalytic performance.Herein,we report iron sites immobilized on defective BiOBr nanosheets as an efficient and selective photocatalyst for activation of O_(2) to singlet oxygen(^(1)O_(2)).These Fe^(3+) species anchored by oxygen vacancies can not only facilitate the separation and migration of photogenerated charge carrier,but also serve as active sites for effective adsorption of 02.Moreover,low-temperature phosphorescence spectra combined with X-ray photoelectron spectroscopy(XPS)and electronic paramagnetic resonance(EPR)spectra under illumination reveal that the Fe species can boost the quantum yield of excited triplet state and accelerate the energy transfer from excited triplet state to adsorbed O2 via a chemical loop of Fe^(3+)/Fe^(2+),thereby achieving highly efficient and selective generation of ^(1)O_(2).As a result,the versatile iron sites on defective BiOBr nanosheets contributes to near-unity conversion rate and selectivity in both aerobic oxidative coupling of amines to imines and sulfoxidation of organic sulfides.This work highlights the significant role of metal sites anchored on semiconductors in regulating the charge/energy transfer during the heterogeneous photocatalytic process,and provides a new angle for designing high-performance photocatalysts.
基金financial support by the Program for the Outstanding Innovative Teams of Higher Learning Institutions of Shanxi(OIT)Shanxi Province Hundred Talent Project
文摘In recent decade, Au nanoclusters of atomic precision (AunLm, where L= organic ligand: thiolate andphosphine) have been shown as a new promising nanogold catalyst. The well-defined AunLm catalystspossess unique electronic properties and frameworks, providing an excellent opportunity to correlate theintrinsic catalytic behavior with the cluster's framework as well as to study the catalytic mechanismsover gold nanoclusters. In this review, we only demonstrate the important roles of the gold nanoclustersin the oxygen activation (e.g., 302 to 102) and their selective oxidations in the presence of oxygen (e.g., COto C02, sulfides to sulfoxides, alcohol to aldehyde, styrene to styrene epoxide, amines to imines, andglucose to gluconic acid). The size-specificity (Au25 (1.3 nm), Au38 (].5 nm), Au144 (1.9 nm), etc.), ligandengineering (e.g., aromatic vs aliphatic), and doping effects (e.g., copper, silver, palladium, and platinum)are discussed in details. Finally, the proposed reactions' mechanism and the relationships of clusters'structure and activity at the atomic level also are presented.
基金supported by the National Natural Science Foundation of China(No.22108043)Natural Science Foundation of Guangdong Province,China(No.2023A1515012711).
文摘Cobalt-rich perovskite oxides play a paramount role in catalyzing oxygen evolution reaction(OER)on account of their acceptable intrinsic activity but are still challenging due to the high costs and undesired stability.In response to the defects,herein,the Mg-incorporated perovskite cobaltite SrCo_(0.6)Fe_(0.3M)g_(0.1)O_(3-δ)(SCFM-0.1)is proposed as a novel earth-abundant and durable OER electrocatalyst.A well-consolidated cubic-symmetry structure and more active oxygen intermediates are enabled upon Mg substitution.Hence,the optimized SCFM-0.1 perovskite oxide achieves prominent OER electrocatalytic performance,that is,a low overpotential of only 320 mV at 10 mA cm^(-2),a small Tafel slope of 65 mV dec^(-1),as well as an outstanding durability within 20 h,substantially outperforming that of the pristine SrCo_(0.7)Fe_(0.3)O_(3-δ)and benchmark Ba_(0.5)Sr_(0.5)Co_(0.8)Fe_(0.2)O_(3-δ)and IrO_(2) catalysts.The strong pHdependent behavior associated with lattice oxygen activation mechanism for SCFM-0.1 catalyst is also confirmed.This work paves a unique avenue to develop cost-effective and robust perovskite cobaltites for efficient OER electrocatalysis.
文摘<img src="Edit_bdc7d851-e537-40df-990c-d678defa9648.png" alt="" />(M = Au, Ag, Cu;<span lang="EN-US" style="font-size:9pt;font-family:"color:black;"><i>n</i></span>= 1, 2, 3) clusters were used as a cluster model to study the activation of oxygen molecules on single-atom catalysts. Structures of <img src="Edit_bb84deb7-e24a-4777-a2f6-a1621ddd2afc.png" alt="" /> clusters were studied by density functional calculations with global optimization. For each <span style="font-family:"color:black;white-space:normal;"><i>n</i></span>, the most stable structures are quite similar for different metal types, and the oxygen molecule prefers to be adsorbed onto M atoms. It is found that the activation degree of oxygen is higher on clusters with non-noble metal Cu than that of Ag or Au containing clusters, by comparing the changes of O-O bond length and vibrational frequency, natural charge population analysis, Fuzzy bond order analysis, and energy barriers of O<sub>2</sub> dissociation. CO oxidation was used as a probe reaction to study the reactivity of Cu-containing clusters, and it is found that the reactivity decreases with the increase of the size of silicon-oxygen clusters. Our results give a new aspect to understand the reaction mechanism of non-precious metal single-atom catalyst for oxygen activation with high efficiency.
基金supported by the National Key Research and Development Program of China (Project No.2018YFB1502903)。
文摘Metal-based perovskite oxides have contributed significantly to the advanced oxidation processes(AOPs)due to their diverse active sites and excellent compositional/structural flexibility.In this study,we specially designed a perovskite oxide with abundant oxygen vacancies,SrCo_(0.8)Fe_(0.2)O_(3)(SCF),and firstly applied it as a catalyst in peroxymonosulfate(PMS) activation towards organic pollutants degradation.The result revealed that the prepared SCF catalyst exhibited excellent performance on organic compounds degradation.Besides,SCF showed much better activity than La_(0.5)Sr_(0.5)Co_(0.8)Fe_(0.2)O_(3)(LSCF) in terms of reaction rate and stability for the degradation of the organic compounds.Based on the analysis of scanning electron microscope,transmission electron microscope,X-ray diffraction,N_(2) adsorption-desorption,X-ray photoelectron spectroscopy and electron paramagnetic resonance,it was confirmed that the perovskite catalysts with high content of Sr doping at A-site could effectively create a defect-rich surface and optimize its physicochemical properties,which was responsible for the excellent heterogeneous catalytic activity of SCF.SCF can generate three highly active species:~1 O_(2),SO_(4)^(-)· and ·OH in PMS activation,revealing the degradation process of organic compounds was a coupled multiple active species in both radical and nonradical pathway.Moreover,it was mainly in a radical pathway in the degradation through PMS activation on SCF and SO_(4)^(-)· radicals produced were the dominant species in SCF/PMS system.This study demonstrated that perovskite-type catalysts could enrich OVs efficiently by doping strategy and regulate the PMS activation towards sulfate radical-based AOPs.
基金supported by the National Natural Science Foundation of China(52261145701 and U21A20162)the 2115 Talent Development Program of China Agricultural University.
文摘The function-led design of porous hydrochar from mineral-rich biowaste for environmental applications inevitably suffers from carbon-ash recalcitrance.However,a method to alter the original carbon skeleton with ash remains elusive and hinders the availability of hydrochar.Herein,we propose a facile strategy for breaking the rigid structure of carbon-ash coupled hydrochar using phase-tunable molten carbonates.A case system was designed in which livestock manure and NaHCO3 were used to prepare the activated hydrochar,and NH3 served as the target contaminant.Due to the redox effect,we found that organic fractions significantly advanced the melting temperature of Na2CO3 below 800℃.The Na species steadily broke the carbon-ash interaction as the thermal intensity increased and transformed inorganic constituents to facilitate ash dissolution,rebuilding the hydrochar skeleton with abundant hierarchical channels and active defect edges.The surface polarity and mesopore distribution collectively governed the five cycles NH3 adsorption attenuation process.Manure hydrochar delivered favorable potential for application with a maximum overall adsorption capacity of 100.49 mg·g^(-1).Integrated spectroscopic characterization and theoretical computations revealed that incorporating NH3 on the carbon surface could transfer electrons to chemisorbed oxygen,which promoted the oxidation of pyridine-N during adsorption.This work offers deep insight into the structure function correlation of hydrochar and inspires a more rational design of engineered hydrochar from high-ash biowaste.
基金funded by the National Natural Science Fundation of China (30840016)the Natural Science Fundation of Jiangsu Province, China (BK 2010310)the Natural Science Fundation for Colleges and Universities in Jiangsu Province, China (10KJB550004)
文摘Peach fruits [Prumus persica (L.) Batsch, cv. Yuhuasanhao] were used as materials to investigate the changes of reactive oxygen species (ROS) and related enzymes in mitochondria respiration during storage and then their influence on senescence of harvested Peach fruits was studied. The results showed that low temperature (5℃) strongly inhibited the reduction of firmness and the increase in respiration rate. During storage at ambient temperature (20℃), ROS had a cumulative process while malondialdehye (MDA) content continued to increase in associated with enhanced membrane lipid peroxidation. Lipoxygenase (LOX) activity was strongly inhibited under the low temperature condition. The activities of succinic dehydrogenase (SDH), cytochrome C oxidase (CCO), and Ca^2+-ATPase declined to a certain extent at ambient temperature, while they showed higher activities at low temperature, which may be related to lower membrane lipid peroxidation at low temperature. Higher Ca^2+ content at ambient temperature may be responsible for impairment of mitochondrial function, thus, leading to fruit senescence. The results showed that under low temperature condition, the low accumulation of ROS and the low level of membrane lipid peroxidation could maintain the function of mitochondria that would help to delay the senescence of peach fruits. These suggested a close relationship existed between ROS metabolism and mitochondrial respiration. It can be inferred that the low temperature helps to delay senescence of peach fruits via suppression of ROS and related enzymes, maintain better homeostasis of Ca^2+ in mitochondria and thus better mitochondrial functions.
基金the National Natural Science Foundation of China ( No.30270933).
文摘The changes in content of Ca2 + and CaM, Ca2 + -ATPase activity and active oxygen metabolism during strawberry (Fragaria ananassa Duch. cv. Chunxing) fruits maturation and senescence were investigated in this study. The results showed that the soluble Ca2+ content and SOD activity in fruits tended to decline and O2 production rate to increase, the Ca2 + -ATPase activity peaked at first and then declined during fruits maturation and senescence. There were the highest CaM content at white stage in preharvest fruits and at marked senescence stage in postharvest ones. The above biochemical changes in fruits stored at low temperature (4℃)were slower than those stored at normal temperature(25℃). Thus, it indicated that the stimulation of calcium messenger system and accumulation of active oxygen free radical were closely related to fruits maturation and senescence.
基金the Key Projects of Shanghai Science and Technology Commission (18JC1412100)the National Natural Science Foundation of China (No. 91745105, 22072092, 92045301)+2 种基金the startup funding provided by Shanghai Tech University for funding their participation in this workfunding provided through The Shell Foundation Grants (No. PT66201)the support from Analytical Instrumentation Center (contract no. SPSTAIC10112914), SPST, Shanghai Tech University。
文摘La_(2)O_(3) catalyzed oxidative coupling of methane(OCM) is a promising process that converts methane directly to valuable C_(2)(ethylene and ethane) products. Our online MS transient study results indicate that pristine surface without carbonate species demonstrates a higher selectivity to C_(2) products, and a lower light-off temperature as well. Further study is focused on carbonate-free La_(2)O_(3) catalyst surface for identification of active oxygen species associated with such products behavior. XPS reveals unique oxygen species with O 1 s binding energy of 531.5 e V correlated with OCM catalytic activity and carbonates removal. However, indicated thermal stability of this species is much higher than the surface peroxide or superoxide structures proposed by earlier computation models. Motivated by experimental results,DFT calculations reveal a new more stable peroxide structure, formed at the subsurface hexacoordinate lattice oxygen sites, with energy 2.18 e V lower than the previous models. The new model of subsurface peroxide provides a perspective for understanding of methyl radicals formation and C_(2) products selectivity in OCM over La_(2)O_(3) catalyst.
基金supported by Innovation Team Project of Northeast Agricultural University of P. R. China (CXZ004-3)Science Foundation of Heilongjiang Province (C2007-16)
文摘Under artificially-simulated complex salt-alkali stress, the levels of active oxygen metabolism in roots were studied using three-year-old cutting seedlings of Spiraea × bumalda ‘Gold Mound' and Spiraea × bumalda ‘Gold Flame'. The present study aimed at exploring the antioxidant capacity in roots of spiraeas and revealing their adaptability to salt-alkali stress. Results indicate that the oxygen free radicals contents, electrolyte leakage rates and MDA contents in roots of Spiraea × bumalda 'Gold Mound' and Spiraea × bumalda 'Gold Flame' show an increasing tendency with the increases of the salinity and pH value, whereas the activities of superoxide dismutase (SOD), peroxidase (POD) and catalase (CAT) all increased firstly and then decreased. With the increase in intensity of salt-alkali stress, the CAT activity in roots of Spiraea × bumalda ‘Gold Flame' is higher and the increasing extents in the oxygen free radicals contents, electrolyte leakage rates as well as MDA contents are lower compared with Spiraea × bumalda ‘Gold Mound', indicating that Spiraea × bumalda ‘Gold Flame' has a stronger antioxidant capacity.
基金Supported by the National Basic Research Program of China under Grant Nos 2010CB327504,2011CB922100 and2011CB301900the National Natural Science Foundation of China under Grant Nos 11104130 and 61322112+2 种基金the Natural Science Foundation of Jiangsu Province under Grant Nos BK2011556 and BK2011050the Priority Academic Program Development of Jiangsu Higher Education Institutionsand the NUPTSF Grant Nos NY213069 and NY214028
文摘The effect of oxygen partial pressure (Po2) during the channel layer deposition on bias stability of amorphous indium-gallium-zinc oxide (a-IGZO) thin film transistors (TFTs) is investigated. As Po2 increases from 10% to 30%, it is found that the device shows enhanced bias stress stability with significantly reduced threshold voltage drift under positive gate bias stress. Based on the x-ray photoelectron spectroscopy measurement, the concentration of oxygen vacancies (Or) within the a-IGZO layer is suppressed by increasing Po2. Meanwhile, the low-frequency noise analysis indicates that the average trap density near the channel/dielectric interface continuously drops with increasing Po2. Therefore, the improved interface quality with increasing Po2 during the channel layer deposition can be attributed to the reduction of interface Ov-related defects, which agrees with the enhanced bias stress stability of the a-IGZO TFTs.
基金the financial support from the office of Vice-President for Research at University of Nevada-Las Vegas
文摘Oxygen transfer presents a serious challenge in the application of liquid lead as a nuclear coolant in advanced reactors. To mitigate corrosion by liquid lead in contact with steel, carefully controlling the oxygen concentration has been used as an effective way. Oxygen needs to mix in liquid lead uniformly and quickly. To enhance oxygen transport in liquid lead, nanoparticles are added to the liquid metal. In the current study, a lattice Boltzmann method is applied to investigate natural convection of copper/lead and aluminum oxide/lead in two-dimensional simplified container. Two thermal boundary cases are evaluated in order to check the effect of different natural convection flow patterns on oxygen transport. Some useful information are obtained such as improvement in natural convection and reduction in oxygen equilibrium time.
基金supported by the National Key Research and Development Program(2016YFA0202500 and 2016YFA0200102)the Natural Scientific Foundation of China(21776019)
文摘The introduction of nitrogen heteroatoms into carbon materials is a facile and efficient strategy to regulate their reactivities and facilitate their potential applications in energy conversion and storage. However,most of nitrogen heteroatoms are doped into the bulk phase of carbon without site selectivity, which significantly reduces the contacts of feedstocks with the active dopants in a conductive scaffold. Herein we proposed the chemical vapor deposition of a nitrogen-doped graphene skin on the 3D porous graphene framework and donated the carbon/carbon composite as surface N-doped grapheme(SNG). In contrast with routine N-doped graphene framework(NGF) with bulk distribution of N heteroatoms, the SNG renders a high surface N content of 1.81 at%, enhanced electrical conductivity of 31 S cm^(-1), a large surface area of 1531 m^2 g^(-1), a low defect density with a low I_D/I_G ratio of 1.55 calculated from Raman spectrum, and a high oxidation peak of 532.7 ℃ in oxygen atmosphere. The selective distribution of N heteroatoms on the surface of SNG affords the effective exposure of active sites at the interfaces of the electrode/electrolyte, so that more N heteroatoms are able to contact with oxygen feedstocks in oxygen reduction reaction or serve as polysulfide anchoring sites to retard the shuttle of polysulfides in a lithium–sulfur battery. This work opens a fresh viewpoint on the manipulation of active site distribution in a conductive scaffolds for multi-electron redox reaction based energy conversion and storage.
文摘The article uses the method of regression statistics to obtain the regression formula of iron fluid nodule ratio Q and compacted graphite ratio R, through rare earth magnesium treatment. At the same time it has given thejudging figure of Q and R, considering oxygen activity and temperature. When using oxygen activity to judgenodule ratio and compacted graphite ratio of the ironfluid treated by rare earth magnesium alloy, its limit value changes with the change of temperature.