A defective iron-based perovskite cathode for high-performance IT-SOFCs:Tailoring the oxygen vacancies using Nb/Ta co-doping

The sluggish kinetics of the electrochemical oxygen reduction reaction(ORR)in intermediatetemperature solid oxide fuel cells(IT-SOFCs)greatly limits the overall cell performance.In this study,an efficient and durable cathode material for IT-SOFCs is designed based on density functional theory(DFT)calculations by co-doping with Nb and Ta the B-site of the SrFeO_(3-δ)perovskite oxide.The DFT calculations suggest that Nb/Ta co-doping can regulate the energy band of the parent SrFeO_(3-δ)and help electron transfer.In symmetrical cells,such cathode with a SrFe_(0.8)Nb_(0.1)Ta_(0.1)O_(3-δ)(SFNT)detailed formula achieves a low cathode polarization resistance of 0.147Ωcm^(2) at 650℃.Electron spin resonance(ESR)and X-ray photoelectron spectroscopy(XPS)analysis confirm that the co-doping of Nb/Ta in SrFeO_(3-δ)B-site increases the balanced concentration of oxygen vacancies,enhancing the electrochemical performance when compared to 20 mol%Nb single-doped perovskite oxide.The cathode button cell with NiSDC|SDC|SFNT configuration achieves an outstanding peak power density of 1.3 W cm^(-2)at 650℃.Moreover,the button cell shows durability for 110 h under 0.65 V at 600℃ using wet H_(2) as fuel.

Thermogravimetric characteristics of corn straw and bituminous coal copyrolysis based the ilmenite oxygen carriers

Herein,the co-pyrolysis reaction characteristics of corn straw(CS)and bituminous coal in the presence of ilmenite oxygen carriers(OCs)are investigated via thermogravimetry coupled with mass spectrometry.The results reveal that the participation of OCs weakens the devolatilization intensity of co-pyrolysis.When the CS blending ratio is<50%,the mixed fuel exhibits positive synergistic effects.The fitting results according to the Coats-Redfern integral method show that the solid-solid interaction between OCs and coke changes the reaction kinetics,enhancing the co-pyrolysis reactivity at the high-temperature zone(750-950C).The synergistic effect is most prominent at a 30%CS blending ratio,with copyrolysis activation energy in the range of 26.35-40.57 kJ·mol^(-1).

Distributions of dissolved oxygen and apparent oxygen utilization in the Cosmonaut Sea and Amundsen Sea in austral summer 2022

Dissolved oxygen(DO)and apparent oxygen utilization(AOU)are essential parameters for evaluating the impact of climate change on marine ecosystems.In this study,we utilized data on DO and AOU collected from the Amundsen Sea(western Antarctic)and the Cosmonaut Sea(eastern Antarctic)during the 38th Chinese National Antarctic Research Expedition,along with chlorophyll a(Chl a)data,to analyze the impact of primary production and the spatial distribution and structural features of water masses in these regions.The findings show that the standard deviation range of parallel DO samples is between 0.1 and 3.9μmol·L^(-1),meeting the precision criteria of the survey method.AOU values lower than 0.0μmol·L^(-1) were commonly observed in the surface waters of both regions,with the highest incidence in the polynya of Amundsen Sea,indicating a strong influence of high primary production.The Cosmonaut Sea exhibited the highest AOU values(higher than 160.0μmol·L^(-1))in the 75-500 m layer,while AOU value in the Amundsen Sea did not exceed 160.0μmol·L^(-1),suggesting potential upwelling of Circumpolar Deep Water to 100 m in the Cosmonaut Sea with minimal changes in its properties,whereas significant changes were noted in the properties of upwelling modified Circumpolar Deep Water in the Amundsen Sea.AOU values lower than 125.0μmol·L^(-1)were detected in the near-bottom waters of the Cosmonaut Sea,indicating the presence of Antarctic Bottom Water.

Toward a comprehensive hypothesis of oxygen-evolution reaction in the presence of iron and gold

This study investigates the effects of Fe on the oxygen-evolution reaction(OER)in the presence of Au.Two distinct areas of OER were identified:the first associated with Fe sites at low overpotential(~330 mV),and the second with Au sites at high overpotential(~870 mV).Various factors such as surface Fe concentration,electrochemical method,scan rate,potential range,concentration,method of adding K_(2)Fe O_(4),nature of Fe,and temperature were varied to observe diverse behaviors during OER for Fe O_(x)H_(y)/Au.Trace amounts of Fe ions had a significant impact on OER,reaching a saturation point where the activity did not increase further.Strong electronic interaction between Fe and Au ions was indicated by X-ray photoelectron spectroscopy(XPS)and electron paramagnetic resonance(EPR)analyses.In situ visible spectroscopy confirmed the formation of Fe O_(4)^(2-)during OER.In situ Mossbauer and surfaceenhanced Raman spectroscopy(SERS)analyses suggest the involvement of Fe-based species as intermediates during the rate-determining step of OER.A lattice OER mechanism based on Fe O_(x)H_(y)was proposed for operation at low overpotentials.Density functional theory(DFT)calculations revealed that Fe oxide,Fe-oxide clusters,and Fe doping on the Au foil exhibited different activities and stabilities during OER.The study provides insights into the interplay between Fe and Au in OER,advancing the understanding of OER mechanisms and offering implications for the design of efficient electrocatalytic systems.

The photosynthetic oxygen evolution does not exclude the important role and contribution of bicarbonate photolysis

Photosynthesis is the most important biochemical reaction on Earth. It has co-evolved and developed with the Earth, driving the biogeochemical cycle of all elements on the planet and serving as the only chemical process in nature that can convert light energy into chemical energy. Some heavy oxygen isotopic(^(18)O) labeling experiments have"conclusively" demonstrated that the oxygen released by photosynthesis comes only from water and are written into textbooks. However, it is not difficult to find that bicarbonate has never been excluded from the direct substrate of photosynthesis from beginning to end during the history of photosynthesis research. No convincing mechanism can be used to explain photosynthetic oxygen evolution solely from water photolysis. The bicarbonate effect, the Dole effect, the thermodynamic convenience of bicarbonate photolysis, the crystal structure characteristics of photosystem Ⅱ, and the reinterpretation of heavy oxygen isotopic labeling(^(18)O)experiments all indicate that the photosynthetic oxygen evolution does not exclude the important role and contribution of bicarbonate photolysis. The recently proposed view that bicarbonate photolysis is the premise of water photolysis, bicarbonate photolysis and water photolysis work together with a 1:1(mol/mol) stoichiometric relationship, and the stoichiometric relationship between oxygen and carbon dioxide released during photosynthetic oxygen evolution is also 1:1, has excellent applicability and objectivity, which can logically and reasonably explain the precise coordination between light and dark reactions during photosynthesis, the bicarbonate effect, the Dole effect, the Kok cycle and the neutrality of water and carbon in nature.This is of great significance for constructing the bionic artificial photosynthetic reactors and scientifically answering the question of the source of elemental stoichiometric relationships in nature.

Veno-arterial extracorporeal membrane oxygenation for the treatment of obstructive shock caused by venous air embolism:A case report

BACKGROUND Venous air embolism(VAE)is a potentially lethal condition,with a reported incidence rate of about 0.13%,and the true incidence may be higher since many VAE are asymptomatic.The current treatments for VAE include Durant's maneuver,aspiration and removal of air through venous catheters,and hyperbaric oxygen therapy.For critically ill patients,use of cardiotonic drugs and chest compressions remain useful strategies.The wider availability of extracorporeal membrane oxygenation(ECMO)has brought a new option for VAE patients.CASE SUMMARY A 53-year-old female patient with VAE presented to the emergency clinic due to abdominal pain with fever for 1 d and unconsciousness for 2 h.One day ago,the patient suffered from abdominal pain,fever,and diarrhea.She suddenly became unconscious after going to the toilet during the intravenous infusion of ciprofloxacin 2 h ago,accompanied by nausea and vomiting,during which a small amount of gastric contents were discharged.She was immediately sent to a local hospital,where cranial and chest computed tomography showed bilateral pneumonia as well as accumulated air visible in the right ventricle and pulmonary artery.The condition deteriorated despite endotracheal intubation,rehydration,and other treatments,and the patient was then transferred to our hospital.Veno-arterial ECMO was applied in our hospital,and the patient's condition gradually improved.The patient was successfully weaned from ECMO and extubated after two days.CONCLUSION ECMO may be an important treatment for patients with VAE in critical condition.

Physical mechanism of oxygen diffusion in the formation of Ga_(2)O_(3) Ohmic contacts

The formation of low-resistance Ohmic contacts in Ga_(2)O_(3) is crucial for high-performance electronic devices. Conventionally, a titanium/gold(Ti/Au) electrode is rapidly annealed to achieve Ohmic contacts, resulting in mutual diffusion of atoms at the interface. However, the specific role of diffusing elements in Ohmic contact formation remains unclear.In this work, we investigate the contribution of oxygen atom diffusion to the formation of Ohmic contacts in Ga_(2)O_(3). We prepare a Ti/Au electrode on a single crystal substrate and conduct a series of electrical and structural characterizations.Using density functional theory, we construct a model of the interface and calculate the charge density, partial density of states, planar electrostatic potential energy, and I–V characteristics. Our results demonstrate that the oxygen atom diffusion effectively reduces the interface barrier, leading to low-resistance Ohmic contacts in Ga_(2)O_(3). These findings provide valuable insights into the underlying mechanisms of Ohmic contact formation and highlight the importance of considering the oxygen atom diffusion in the design of Ga_(2)O_(3)-based electronic devices.

Accidental placement of venous return catheter in the superior vena cava during venovenous extracorporeal membrane oxygenation for severe pneumonia: A case report

BACKGROUND Venovenous extracorporeal membrane oxygenation(V-V ECMO)has become an important treatment for severe pneumonia,but there are various complications during the treatment.This article describes a case with severe pneumonia success-fully treated by V-V ECMO,but during treatment,the retrovenous catheter,which was supposed to be in the right internal vein,entered the superior vena cava directly in the mediastinum.The ECMO was safely withdrawn after multidiscip-linary consultation.Our experience with this case is expected to provide a reference for colleagues who will encounter similar situations.CASE SUMMARY A 64-year-old man had severe pulmonary infection and respiratory failure.He was admitted to our hospital and was given ventilation support(fraction of inspired oxygen 100%).The respiratory failure was not improved and he was treated by V-V ECMO,during which the venous return catheter,which was supposed to be in the right internal vein,entered the superior vena cava directly in the mediastinum.There was a risk of massive mediastinal bleeding if the catheter was removed directly when the ECMO was withdrawn.Finally,the patient underwent vena cava angiography+balloon attachment+ECMO with-drawal in the operating room(prepared for conversion to thoracotomy for vascular exploration and repair at any time during surgery)after multidiscip-linary consultation.ECMO was safely withdrawn,and the patient recovered and was discharged.CONCLUSION Patients may have different vascular conditions.Multidisciplinary cooperation can ensure patient safety.Our experience will provide a reference for similar cases.

CO_(2)capture costs of chemical looping combustion of biomass:A comparison of natural and synthetic oxygen carrier

Chemical looping combustion has the potential to be an efficient and low-cost technology capable of contributing to the reduction of the atmospheric concentration of CO_(2) in order to reach the 1.5/2°C goal and mitigate climate change.In this process,a metal oxide is used as oxygen carrier in a dual fluidized bed to generate clean CO_(2) via combustion of biomass.Most commonly,natural ores or synthetic materials are used as oxygen carrier whereas both must meet special requirements for the conversion of solid fuels.Synthetic oxygen carriers are characterized by higher reactivity at the expense of higher costs versus the lower-cost natural ores.To determine the viability of both possibilities,a techno-economic comparison of a synthetic material based on manganese,iron,and copper to the natural ore ilmenite was conducted.The synthetic oxygen carrier was characterized and tested in a pilot plant,where high combustion efficiencies up to 98.4%and carbon capture rates up to 98.5%were reached.The techno-economic assessment resulted in CO_(2) capture costs of 75 and 40€/tCO_(2) for the synthetic and natural ore route respectively,whereas a sensitivity analysis showed the high impact of production costs and attrition rates of the synthetic material.The synthetic oxygen carrier could break even with the natural ore in case of lower production costs and attrition rates,which could be reached by adapting the production process and recycling material.By comparison to state-of-the-art technologies,it is demonstrated that both routes are viable and the capture cost of CO_(2) could be reduced by implementing the chemical looping combustion technology.

Tuning the crystalline and electronic structure of ZrO_(2)via oxygen vacancies and nano-structuring for polysulfides conversion in lithium-sulfur batteries

The recent emergence of tetragonal phases zirconium dioxide(ZrO_(2))with vacancies has generated significant interest as a highly efficient and stable electrocatalyst with potential applications in trapping polysulfides and facilitating rapid conversion in lithium-sulfur batteries(LSBs).However,the reduction of ZrO_(2)is challenging,even under strong reducing atmospheres at high temperatures and pressures.Consequently,the limited presence of oxygen vacancies results in insufficient active sites and reaction interfaces,thereby hindering practical implementation.Herein,we successfully introduced abundant oxygen vacancies into ZrO_(2)at the nanoscale with the help of carbon nanotubes(CNTs-OH)through hydrogen-etching at lower temperatures and pressures.The introduced oxygen vacancies on ZrO_(2-x)/CNTs-OH can effectively rearrange charge distribution,enhance sulfiphilicity and increase active sites,contributing to high ionic and electronic transfer kinetics,strong binding energy and low redox barriers between polysulfides and ZrO_(2-x).These findings have been experimentally validated and supported by theory calculations.As a result,LSBs assembled with the ZrO_(2-x)/CNTs-OH modified separators demonstrate excellent rate performance,superior cycling stability,and ultra-high sulfur utilization.Especially,at high sulfur loading of 6 mg cm^(-2),the area capacity is still up to 6.3 mA h cm^(-2).This work provides valuable insights into the structural and functional optimization of electrocatalysts for batteries.

Increased Oxygen Vacancies in CuO-ZnO Snowflake-like Composites Drive the Hydrogenation of CO_(2) to Methanol

Cu/ZnO is widely used in the hydrogenation of carbon dioxide (CO_(2)) to methanol (CH_(3)OH) to improve the lowconversion rate and selectivity generally observed. In this work, a series of In, Zr, Co, and Ni-doped CuO-ZnO catalysts wassynthesized via a hydrothermal method. By introducing a second metal element, the activity and dispersion of the activesites can be adjusted and the synergy between the metal and the carrier can be enhanced, forming an abundance of oxygenvacancies. Oxygen vacancies not only adsorb CO_(2) but also activate the intermediates in methanol synthesis, playing a keyrole in the entire reaction. Co3O4-CuO-ZnO had the best catalytic performance (a CO_(2) conversion rate of 9.17%;a CH_(3)OHselectivity of 92.77%). This study describes a typical strategy for multi-component doping to construct a catalyst with anabundance of oxygen vacancies, allowing more effective catalysis to synthesize CH_(3)OH from CO_(2).

The Performance of Extracorporeal Membrane Oxygenation in Various Viral Pneumonia Pandemics: A Meta-Analysis and Systematic Review

Objective: To compare the effects of extracorporeal membrane oxygenation (ECMO) and routine mechanical ventilation on mortality and the risk of associated adverse events in patients with severe viral pneumonia. Methods: PubMed, the Cochrane Library, Embase, Web of Science, and other databases were searched to collect case-control or cohort studies on prognoses associated with ECMO treatment for viral pneumonia. Search terms included extracorporeal membrane oxygenation, ECMO, viral pneumonia, COVID-19, influenza, MERS, and others. According to the PICOS principle, two evaluators independently screened the literature, extracted the data, cross-checked the data, and extracted the data again. Two researchers evaluated the risk of bias in the included studies according to the Newcastle-Ottawa Scale (NOS) and cross-checked the results. Meta-analysis was performed using RevMan 5.3 software. Results: Nine studies were included for analysis, encompassing a total of 4,330 patients, which were categorized into ECMO and CMV groups. There were no significant differences between the two groups in most baseline data;however, the ECMO group had a lower oxygenation index, and some studies reported higher SOFA scores in the ECMO group compared to the CMV group. There was no significant difference in in-hospital mortality between the two groups. The length of ICU stay, total hospital stay, and total mechanical ventilation time were longer in the ECMO group than in the CMV group. In terms of adverse events, there was no significant difference in the occurrence of kidney injury between the two groups. Bleeding events were reported in two studies, with more bleeding events occurring in the ECMO group. According to the subgroup analysis of different virus types, there were no statistical differences in the above aspects among patients with swine flu, novel coronavirus, and MERS. Conclusion: ECMO has a certain degree of positive significance in the treatment of severe viral pneumonia, but there is no significant difference in the treatment outcome of ECMO across different epidemic periods. The timing of ECMO treatment, patient management, and withdrawal evaluation still need further research.

Co/CoO heterojunction rich in oxygen vacancies introduced by O_(2) plasma embedded in mesoporous walls of carbon nanoboxes covered with carbon nanotubes for rechargeable zinc-air battery

Herein,Co/CoO heterojunction nanoparticles(NPs)rich in oxygen vacancies embedded in mesoporous walls of nitrogen-doped hollow carbon nanoboxes coupled with nitrogen-doped carbon nanotubes(P-Co/CoOV@NHCNB@NCNT)are well designed through zeolite-imidazole framework(ZIF-67)carbonization,chemical vapor deposition,and O_(2) plasma treatment.As a result,the threedimensional NHCNBs coupled with NCNTs and unique heterojunction with rich oxygen vacancies reduce the charge transport resistance and accelerate the catalytic reaction rate of the P-Co/CoOV@NHCNB@NCNT,and they display exceedingly good electrocatalytic performance for oxygen reduction reaction(ORR,halfwave potential[EORR,1/2=0.855 V vs.reversible hydrogen electrode])and oxygen evolution reaction(OER,overpotential(η_(OER,10)=377mV@10mA cm^(−2)),which exceeds that of the commercial Pt/C+RuO_(2) and most of the formerly reported electrocatalysts.Impressively,both the aqueous and flexible foldable all-solid-state rechargeable zinc-air batteries(ZABs)assembled with the P-Co/CoOV@NHCNB@NCNT catalyst reveal a large maximum power density and outstanding long-term cycling stability.First-principles density functional theory calculations show that the formation of heterojunctions and oxygen vacancies enhances conductivity,reduces reaction energy barriers,and accelerates reaction kinetics rates.This work opens up a new avenue for the facile construction of highly active,structurally stable,and cost-effective bifunctional catalysts for ZABs.

Microwave shock motivating the Sr substitution of 2D porous GdFeO_(3) perovskite for highly active oxygen evolution

The incorporation of partial A-site substitution in perovskite oxides represents a promising strategy for precisely controlling the electronic configuration and enhancing its intrinsic catalytic activity.Conventional methods for A-site substitution typically involve prolonged high-temperature processes.While these processes promote the development of unique nanostructures with highly exposed active sites,they often result in the uncontrolled configuration of introduced elements.Herein,we present a novel approach for synthesizing two-dimensional(2D)porous GdFeO_(3) perovskite with A-site strontium(Sr)substitution utilizing microwave shock method.This technique enables precise control of the Sr content and simultaneous construction of 2D porous structures in one step,capitalizing on the advantages of rapid heating and cooling(temperature~1100 K,rate~70 K s^(-1)).The active sites of this oxygen-rich defect structure can be clearly revealed through the simulation of the electronic configuration and the comprehensive analysis of the crystal structure.For electrocatalytic oxygen evolution reaction application,the synthesized 2D porous Gd_(0.8)Sr_(0.2)FeO_(3) electrocatalyst exhibits an exceptional overpotential of 294 mV at a current density of 10 mA cm^(-2)and a small Tafel slope of 55.85 mV dec^(-1)in alkaline electrolytes.This study offers a fresh perspective on designing crystal configurations and the construction of nanostructures in perovskite.

Optimizing 3d spin polarization of CoOOH by in situ Mo doping for efficient oxygen evolution reaction

Transition-metal oxyhydroxides are attractive catalysts for oxygen evolution reactions(OERs).Further studies for developing transition-metal oxyhydroxide catalysts and understanding their catalytic mechanisms will benefit their quick transition to the next catalysts.Herein,Mo-doped CoOOH was designed as a high-performance model electrocatalyst with durability for 20 h at 10 mAcm−2.Additionally,it had an overpotential of 260 mV(glassy carbon)or 215 mV(nickel foam),which was 78 mV lower than that of IrO_(2)(338 mV).In situ,Raman spectroscopy revealed the transformation process of CoOOH.Calculations using the density functional theory showed that during OER,doped Mo increased the spin-up density of states and shrank the spin-down bandgap of the 3d orbits in the reconstructed CoOOH under the electrochemical activation process,which simultaneously optimized the adsorption and electron conduction of oxygen-related intermediates on Co sites and lowered the OER overpotentials.Our research provides new insights into the methodical planning of the creation of transition-metal oxyhydroxide OER catalysts.

Single-atom catalysts for the electrochemical reduction of carbon dioxide into hydrocarbons and oxygenates

The electrochemical reduction of carbon dioxide offers a sound and economically viable technology for the electrification and decarbonization of the chemical and fuel industries.In this technology,an electrocatalytic material and renewable energy-generated electricity drive the conversion of carbon dioxide into high-value chemicals and carbon-neutral fuels.Over the past few years,single-atom catalysts have been intensively studied as they could provide near-unity atom utilization and unique catalytic performance.Single-atom catalysts have become one of the state-of-the-art catalyst materials for the electrochemical reduction of carbon dioxide into carbon monoxide.However,it remains a challenge for single-atom catalysts to facilitate the efficient conversion of carbon dioxide into products beyond carbon monoxide.In this review,we summarize and present important findings and critical insights from studies on the electrochemical carbon dioxide reduction reaction into hydrocarbons and oxygenates using single-atom catalysts.It is hoped that this review gives a thorough recapitulation and analysis of the science behind the catalysis of carbon dioxide into more reduced products through singleatom catalysts so that it can be a guide for future research and development on catalysts with industry-ready performance for the electrochemical reduction of carbon dioxide into high-value chemicals and carbon-neutral fuels.

Activation of the wnt/β-catenin/CYP1B1 pathway alleviates oxidative stress and protects the blood-brain barrier under cerebral ischemia/reperfusion conditions

Accumulating evidence suggests that oxidative stress and the Wnt/β-catenin pathway participate in stroke-induced disruption of the blood-brain barrier.However,the potential links between them following ischemic stroke remain largely unknown.The present study found that cerebral ischemia leads to oxidative stress and repression of the Wnt/β-catenin pathway.Meanwhile,Wnt/β-catenin pathway activation by the pharmacological inhibito r,TWS119,relieved oxidative stress,increased the levels of cytochrome P4501B1(CYP1B1)and tight junction-associated proteins(zonula occludens-1[ZO-1],occludin and claudin-5),as well as brain microvascular density in cerebral ischemia rats.Moreove r,rat brain microvascular endothelial cells that underwent oxygen glucose deprivation/reoxygenation displayed intense oxidative stress,suppression of the Wnt/β-catenin pathway,aggravated cell apoptosis,downregulated CYP1B1and tight junction protein levels,and inhibited cell prolife ration and migration.Overexpression ofβ-catenin or knockdown ofβ-catenin and CYP1B1 genes in rat brain mic rovascular endothelial cells at least partly ameliorated or exacerbated these effects,respectively.In addition,small interfering RNA-mediatedβ-catenin silencing decreased CYP1B1 expression,whereas CYP1B1 knoc kdown did not change the levels of glycogen synthase kinase 3β,Wnt-3a,andβ-catenin proteins in rat brain microvascular endothelial cells after oxygen glucose deprivatio n/reoxygenation.Thus,the data suggest that CYP1B1 can be regulated by Wnt/β-catenin signaling,and activation of the Wnt/β-catenin/CYP1B1 pathway contributes to alleviation of oxidative stress,increased tight junction levels,and protection of the blood-brain barrier against ischemia/hypoxia-induced injury.

Paradoxical herniation associated with hyperbaric oxygen therapy after decompressive craniectomy: A case report

BACKGROUND Whether hyperbaric oxygen therapy(HBOT)can cause paradoxical herniation is still unclear.CASE SUMMARY A 65-year-old patient who was comatose due to brain trauma underwent decompressive craniotomy and gradually regained consciousness after surgery.HBOT was administered 22 d after surgery due to speech impairment.Paradoxical herniation appeared on the second day after treatment,and the patient’s condition worsened after receiving mannitol treatment at the rehabilitation hospital.After timely skull repair,the paradoxical herniation was resolved,and the patient regained consciousness and had a good recovery as observed at the follow-up visit.CONCLUSION Paradoxical herniation is rare and may be caused by HBOT.However,the underlying mechanism is unknown,and the understanding of this phenomenon is insufficient.The use of mannitol may worsen this condition.Timely skull repair can treat paradoxical herniation and prevent serious complications.

Investigating the impact of dynamic structural changes of Au/rutile catalysts on the catalytic activity of CO oxidation

The surface properties of oxidic supports and their interaction with the supported metals play critical roles in governing the catalytic activities of oxide‐supported metal catalysts.When metals are supported on reducible oxides,dynamic surface reconstruction phenomena,including strong metal–support interaction(SMSI)and oxygen vacancy formation,complicate the determination of the structural–functional relationship at the active sites.Here,we performed a systematic investigation of the dynamic behavior of Au nanocatalysts supported on flame‐synthesized TiO_(2),which takes predominantly a rutile phase,using CO oxidation above room temperature as a probe reaction.Our analysis conclusively elucidated a negative correlation between the catalytic activity of Au/TiO_(2) and the oxygen vacancy at the Au/TiO_(2) interface.Although the reversible formation and retracting of SMSI overlayers have been ubiquitously observed on Au/TiO_(2) samples,the catalytic consequence of SMSI remains inconclusive.Density functional theory suggests that the electron transfer from TiO_(2) to Au is correlated to the presence of the interfacial oxygen vacancies,retarding the catalytic activation of CO oxidation.

Genesis of LCT Pegmatites during Early Paleozoic Orogeny of the North Qinling Orogenic Belt,China:Emplacement Conditions and Structural Control

The Guanpo pegmatite field in the North Qinling orogenic belt(NQB),China,hosts the most abundant LCT pegmatites.However,their emplacement conditions and structural control remain unexplored.In this contribution,we investigated it combining pegmatite orientation measurement with oxygen isotope geothermometry and fluid inclusion study.The orientations of type A1 pegmatites(P_(f)<σ_(2))are predominantly influenced by P-and T-fractures due to simple shearing in Shiziping dextral thrust shear zone during D_(2)deformation,whereas type A2 pegmatites(contemporaneous with D_(4))are governed by hydraulic fractures aligned with S_(0)and S_(0+1)stemming from fluid pressure(P_(f)<σ_(2)).Additionally,type B pegmatites(P_(f)≤σ_(2))exhibit orientations shaped by en echelon extensional fractures in local ductile shear zones(contemporaneous with D_(3)).The albite-quartz oxygen isotope geothermometry and microthermometric analysis of fluid inclusions in elbaites from the latest pegmatites(including types B and A2)suggest that the crystallization P-T for late magmatic and hydrothermal stages are 527.5-559.2℃,320℃,3.1-3.6 kbar and 2.0 kbar,respectively.Our observations along with previous studies suggest that the genesis of the LCT pegmatites was a long-term,multi-stage event during early Paleozoic orogeny(including the collision stage)of the NQB,and was facilitated by various local fractures.