Commonly Existing Hole-Capturer Organics Adsorption-Induced Recombination over Metal/Semiconductor Perimeters: A Possible Important Factor Affecting Photocatalytic Efficiencies.

Photocatalysis is a physiochemical effect arising from the relaxation of photoinduced electrons from the conduction band to the valence band. Controlling the electron relaxation to occur through photocatalytic pathways and prohibiting other relaxations is the main scientific thought for photocatalytic studies. It is needed to know the parallel relaxation pathways that can compete with photocatalytic reactions. By means of in situ photoconductances (PCs) and photoinduced absorptions (PAs), the current research studied the photoinduced electron relaxations of the Au/TiO2 in different atmospheres and at different temperatures. The PC and PA relaxations became different and fast when methanol, ethanol, isopropanol, and acetone were introduced; they also tend to decrease as temperature increases, while that of the undecorated TiO2 in all atmospheres and the Au/TiO2 in pure N2 increased. The results indicated that the organic adsorptions over the Au/TO2 perimeters change the relaxation pathway, and a hole-capturing organics adsorption-induced recombination over the Au/TiO2 perimeter was proposed to explain the relaxations. We found that this relaxation also exists for Ag/TiO2, Pt/TiO2, and Au/ZnO, so it is a commonly existing physical course for the metal/semiconductor (M/S) materials. The effect of the organics and M/S structures on the relaxation was discussed, and the relationship with photocatalytic reactions was also analyzed. Our finding means that blocking this relaxation pathway is an effective way to increase photocatalytic activities, which might open a door for highly active photocatalyst developments.

Kinetic pathways of sub-bandgap induced electron transfer in Ag/TiO2 and the effect on isopropanol dehydrogenation under gaseous conditions.

Electron transfer and its kinetics play a major role in the photocatalysis of metal/semiconductor systems. Using in situ photoconductances, in situ photoabsorption, and photoinduced spectroscopic techniques, the present research aimed to gain a deep insight into electron transfer pathways and their kinetics for Ag/TiO2 systems under sub-bandgap light illumination and gaseous conditions. The results revealed that electrons generated in TiO2 can transfer to Ag nanoparticles at fast rates, and plasmon-generated electrons in Ag nanoparticles can also transfer to TiO2. However, it was found that plasmon-assisted hot electron transfer efficiency is much lower than the electron transition from the valence band to the conduction band of TiO2. Rather than plasmonic active spots, the results showed that Ag nanoparticles acted as co-catalyst sites bridging electron transfer to recombination in a methanol-containing N2 atmosphere. As a result, photocatalytic isopropanol dehydrogenation was decreased. Independent of Ag decorations, it was also indicated that isopropanol dehydrogenation mainly occurred over TiO2 surfaces; therefore, Ag nanoparticles did not increase photocatalytic activities. Our results may provide a different viewpoint on sub-bandgap light-induced Ag/TiO2 photocatalysis under gaseous conditions; this may also facilitate the understanding of the photocatalytic mechanism of metal/semiconductor systems.

Fermi-level shift, electron separation, and plasmon resonance change in Ag nanoparticle-decorated TiO2 under UV light illumination.

Noble metal nanoparticles are widely used as co-catalysts for storing and separating electrons in semiconductor photocatalysis. Thus, evaluating this ability is important and meaningful to understand the photocatalytic mechanism. Employing Ag nanoparticles, the present study combined in situ photoconductance and theoretical analysis to evaluate the Fermi-level (EF) shift in a UV-illuminated Ag/TiO2 system under gaseous conditions. Based on this, the role of the Ag nanoparticles in storing and separating electrons was discussed. It was found that the EF of Ag/TiO2 is located deeper in the gap and a variation in temperature has less effect on the EF of Ag/TiO2 compared to the undecorated TiO2. The analysis showed that ∼46 electrons can be stored in 10 nm Ag nanoparticles under our experimental conditions, which does not change with temperature. The electron traps in TiO2 can affect the electron distribution in the TiO2 and Ag nanoparticles. It was observed that the localized surface plasmon resonance (LSPR) of the Ag nanoparticles exhibited a blue-shift under UV light illumination, which is generally ascribed to the electron storage in the Ag nanoparticles. However, we showed that the blue-shift is not related to the electron storage in the Ag nanoparticles, and thus it cannot be used as an indicator for evaluating their electron-storage ability. The in situ XPS analysis also does not support that the LSPR blue shift is associated with the reduction in the Ag2O layer and TiO2.

A light-heat synergism in the sub-bandgap photocatalytic response of pristine TiO2: a study of in situ diffusion reflectance and conductance.

Pristine TiO2 materials are mainly used as photocatalysts under super-bandgap light illumination. The sub-bandgap (SBG) photocatalytic response has seldom been investigated and the mechanism of action remains unclear. In the current research, we firstly study the SBG light electronic transition of pristine P25 TiO2 by means of in situ diffusion reflectance and (photo)conductance measurements under finely controllable conditions. It is revealed that the SBG light can promote valence band (VB) electrons to the exponentially-distributed gap states of the TiO2, which can then be thermally activated to the CB states. A hole in the VB and an electron in the CB can be generated by the synergism of a SBG photon and heat. It is also seen that the photoinduced electrons can transfer to O2 through the CB states, and that the holes can be captured by isopropanol molecules. As a result, isopropanol dehydrogenation can occur over pristine TiO2 under SBG light illumination. It is seen that the photocatalytic activity increases with temperature and the energy of the SBG photons, in agreement with the light-heat synergistic electric transition via the exponential gap states. The present research reveals a mechanism for the SBG light photocatalytic response of pristine TiO2 materials, which is important in designing highly-active visible light active photocatalysts.

Directed Accumulation of Nitrogen Metabolites through Processing Endows Wuyi Rock Tea with Singular Qualities.

The execution of specific processing protocols endows Wuyi rock tea with distinctive qualities produced through signature metabolic processes. In this work, tea leaves were collected before and after each of three processing stages for both targeted and untargeted metabolomic analysis. Metabolic profiles of processing stages through each processing stage of rotation, pan-firing and roasting were studied. Overall, 614 metabolites were significantly altered, predominantly through nitrogen- enriching (N) pathways. Roasting led to the enrichment of 342 N metabolites, including 34 lipids, 17 organic acids, 32 alkaloids and 25 amino acids, as well as secondary derivatives beneficial for tea quality. This distinctive shift towards enrichment of N metabolites strongly supports concluding that this directed accumulation of N metabolites is how each of the three processing stages endows Wuyi rock tea with singular quality.

Kinetics and energetic analysis of the slow dispersive electron transfer from nano-TiO2 to O2 by in situ diffusion reflectance and Laplace transform.

Electron transfer to O2 is a universally existing process for the physiochemistry of many materials. Electron transfer to O2 is also an inevitable process for photocatalytic reactions over TiO2 and other materials. In the present research, a diffusion reflectance system was developed to measure in situ optical diffusion reflectances caused by photoinduced electrons in nano-TiO2 under a steady light illumination; in situ absorption decays can be obtained to study the electron transfer from their trapped states to O2. It is seen that the kinetics of electron transfer to O2 is persistent and dispersive; this lasts for several minutes and approximately agrees with a stretched exponential kinetics. The result implies that variable apparent energy barriers (Eis) are involved in the electron transfer. The effects of O2 amount, light intensity, and temperature are studied and the results mean the trap-filling effect should be involved in the electron transfer to O2. A Laplace transform is used to derive the Ei distributions. It is found that the Ei dispersion shape almost does not change; this indicates that the physical reason causing the Ei dispersion is the same for different experimental conditions and possibly comes from the trap-filling effect. It is shown that the slow kinetics of the electron transfer is also dependent on the slow rate for an electron transferring from a trap to O2, in additional to the trapping-filling effect. The results indicate that the photocatalytic activity can be increased through a modulation in trap distribution.

The effect of Cu dopants on electron transfer to O2 and the connection with acetone photocatalytic oxidations over nano-TiO2.

Modifying TiO2 with the Cu element has been shown to be useful for photocatalysis. Although it had been known that Cu species could trap electrons from TiO2, whether they can affect the kinetics of electron transfer and how this can contribute to photocatalysis still remain unknown. In the current research, Cu-TiO2 samples were firstly prepared with a hydrothermal reaction and characterized in detail. It was shown that Cu elements were doped in the TiO2 lattice in +1/0 valence states and have a minor effect on the TiO2 structure. By means of photoconductances, it is shown that the Cu dopants could catalyze the electron transfer from TiO2 to O2 by reducing the apparent activation energy (Eapp) by about 2 times. The photocatalytic experiments conducted at different temperatures showed that the Eapp of the acetone photocatalytic oxidations could be decreased by ∼2 times; this implies that the Cu dopants change the photocatalytic pathway. First-principles computation showed that the surface Cu dopants, along with the compensated oxygen vacancies, can mediate both of the electron and hole transfer. By combining other studies, we proposed that the Cu sites could act as Lewis acid and base pairs that could combine with acetone and O2 molecules under UV light illumination; this allows electron transfer to O2via the Cu sites that then react with acetone. As compared to pure TiO2 surfaces, the different chemical environment of the Cu sites leads to the decrease in the Eapp of photocatalysis.

CdS/ZnS Heterostructured Porous Composite with Enhanced Visible Light Photocatalysis.

Fabrication of semiconductor composites consisting of multicomponent or multiphase heterojunctions is a very effective strategy to design highly active photocatalyst systems. Here we present a facile design to fabricate novel CdS/ZnS heterostructured porous sheet-like nanocomposite based on a cation-exchanged hydrothermal procedure. Micro-structural analyses reveal that the product is a kind of heterostructured composite with porous structure and high crystallinity. The composite nanosheets exhibited enhanced visible-light photoactivity compared with pure ZnS or CdS. Among them, sample of Cd0.45Zn0.55S gave the highest degradation rate of about 99% under visible-light irradiation within 60 min when 10 mg of the sample was added into 50 mL of methyl orange in aqueous solution (10 mg/L). The enhanced photocatalytic activity was presumed to result from the direct photoinduced interfacial charge transfer (IFCT) from the valence band (VB) of ZnS to CdS.

Effects of spatial topologies and electron Fermi-level gradient on the photocatalytic efficiency of nano-particulate semiconductors.

Nanocrystalline (nc) semiconductor materials are important in photocatalysis. The nanoparticle (NP) topologies and electron Fermi-level (EF) gradient along the interconnected NPs affect the photocatalytic efficiency (η) of the nc-materials because of the charge carrier interparticle transport (IPT). However, the detailed physiochemical kinetic mechanism remains unclear. Based on the kinetic analysis and the numerical Monte-Carlo simulation of random walks, the statistical probability distributions pRec(t) and pit(t) for the recombination time and interfacial transfer (IT) time have been proposed in this study. The recombination lifetime (τRed) and IT lifetime (τIT) were calculated by averaging pRec(t) and pit(t). The characteristic time τe of the entire electron kinetics was defined using τRe and τIT, and η was calculated by dividing τe by τIT. The simulation results show that the pRec(t) clearly shows the IPT of electrons. Both the kinetic factors (NP spatial topologies and boundary barrier) and the thermodynamic factor (electron EF gradient) can affect the IPT. It was observed that the increase in IPT cannot lead to a monotonous increase in η although it can prohibit recombination. Whether the IPT can increase the η is dependent on ratio of the back IPT for recombination and the forward IPT for IT. The existence of an electron EF gradient from the electron generation site to the active site can increase η by promoting the forward IPT.

The role of electron interfacial transfer in mesoporous nano-TiO2 photocatalysis: a combined study of in situ photoconductivity and numerical kinetic simulation.

In this research, a combination of in situ photoconductivity (σ) and kinetic simulations was used to study the role of electron interfacial transfer (IT) in the gaseous photocatalysis of formic acid by mesoporous nanocrystalline TiO2. The effects of light intensity, initial formic acid concentrations, oxygen amounts, and temperature on the in situ σ and the photocatalytic courses were studied in detail. The temperature dependence of in situ σ clearly shows that the electron transfer is determined by the IT of electrons to O2 rather than by the transport. It was seen that the electron IT limits the photocatalysis by correlating with the recombination and the hole IT via the dynamic change in electron densities. The numerical simulation of in situ σ shows that the IT of electrons belongs to a thermally activated process that presents a thermal barrier of 0.5 eV. It is considered that this high thermal barrier limits the IT of electrons. It was also seen that the thermal activation of photocatalysis does not relate to that of the electron IT, although the overall photocatalysis is limited by the IT of electrons. Our finding shows that it is an effective way to increase the photocatalytic activity by reducing the thermal barrier of electron IT.

Monte-Carlo modelling of nano-material photocatalysis: bridging photocatalytic activity and microscopic charge kinetics.

In photocatalysis, it is known that light intensity, organic concentration, and temperature affect the photocatalytic activity by changing the microscopic kinetics of holes and electrons. However, how the microscopic kinetics of holes and electrons relates to the photocatalytic activity was not well known. In the present research, we developed a Monte-Carlo random walking model that involved all of the charge kinetics, including the photo-generation, the recombination, the transport, and the interfacial transfer of holes and electrons, to simulate the overall photocatalytic reaction, which we called a "computer experiment" of photocatalysis. By using this model, we simulated the effect of light intensity, temperature, and organic surface coverage on the photocatalytic activity and the density of the free electrons that accumulate in the simulated system. It was seen that the increase of light intensity increases the electron density and its mobility, which increases the probability for a hole/electron to find an electron/hole for recombination, and consequently led to an apparent kinetics that the quantum yield (QY) decreases with the increase of light intensity. It was also seen that the increase of organic surface coverage could increase the rate of hole interfacial transfer and result in the decrease of the probability for an electron to recombine with a hole. Moreover, the increase of organic coverage on the nano-material surface can also increase the accumulation of electrons, which enhances the mobility for electrons to undergo interfacial transfer, and finally leads to the increase of photocatalytic activity. The simulation showed that the temperature had a more complicated effect, as it can simultaneously change the activation of electrons, the interfacial transfer of holes, and the interfacial transfer of electrons. It was shown that the interfacial transfer of holes might play a main role at low temperature, with the temperature-dependence of QY conforming to the Arrhenius model. The activation of electrons from the traps to the conduction band might become important at high temperature, which accelerates the electron movement for recombination and leads to a temperature dependence of QY that deviates from the Arrhenius model.

A stochastic study of electron transfer kinetics in nano-particulate photocatalysis: a comparison of the quasi-equilibrium approximation with a random walking model.

In the photocatalysis of porous nano-crystalline materials, the transfer of electrons to O2 plays an important role, which includes the electron transport to photocatalytic active centers and successive interfacial transfer to O2. The slowest of them will determine the overall speed of electron transfer in the photocatalysis reaction. Considering the photocatalysis of porous nano-crystalline TiO2 as an example, although some experimental results have shown that the electron kinetics are limited by the interfacial transfer, we still lack the depth of understanding the microscopic mechanism from a theoretical viewpoint. In the present research, a stochastic quasi-equilibrium (QE) theoretical model and a stochastic random walking (RW) model were established to discuss the electron transport and electron interfacial transfer by taking the electron multi-trapping transport and electron interfacial transfer from the photocatalytic active centers to O2 into consideration. By carefully investigating the effect of the electron Fermi level (EF) and the photocatalytic center number on electron transport, we showed that the time taken for an electron to transport to a photocatalytic center predicated by the stochastic RW model was much lower than that predicted by the stochastic QE model, indicating that the electrons cannot reach a QE state during their transport to photocatalytic centers. The stochastic QE model predicted that the electron kinetics of a real photocatalysis for porous nano-crystalline TiO2 should be limited by electron transport, whereas the stochastic RW model showed that the electron kinetics of a real photocatalysis can be limited by the interfacial transfer. Our simulation results show that the stochastic RW model was more in line with the real electron kinetics that have been observed in experiments, therefore it is concluded that the photoinduced electrons cannot reach a QE state before transferring to O2.

Correlation of electron transport and photocatalysis of nanocrystalline clusters studied by Monte-Carlo continuity random walking.

In this research, Monte-Carlo Continuity Random Walking (MC-RW) model was used to study the relation between electron transport and photocatalysis of nano-crystalline (nc) clusters. The effects of defect energy disorder, spatial disorder of material structure, electron density, and interfacial transfer/recombination on the electron transport and the photocatalysis were studied. Photocatalytic activity is defined as 1/τ from a statistical viewpoint with τ being the electron average lifetime. Based on the MC-RW simulation, a clear physical and chemical "picture" was given for the photocatalytic kinetic analysis of nc-clusters. It is shown that the increase of defect energy disorder and material spatial structural disorder, such as the decrease of defect trap number, the increase of crystallinity, the increase of particle size, and the increase of inter-particle connection, can enhance photocatalytic activity through increasing electron transport ability. The increase of electron density increases the electron Fermi level, which decreases the activation energy for electron de-trapping from traps to extending states, and correspondingly increases electron transport ability and photocatalytic activity. Reducing recombination of electrons and holes can increase electron transport through the increase of electron density and then increases the photocatalytic activity. In addition to the electron transport, the increase of probability for electrons to undergo photocatalysis can increase photocatalytic activity through the increase of the electron interfacial transfer speed.

Kinetic study of the heterogeneous photocatalysis of porous nanocrystalline TiO2 assemblies using a continuous random walk simulation.

The continuous time random walk (CTRW) simulation was used to study the photocatalytic kinetics of nanocrystalline (nc)-TiO2 assemblies in this research. nc-TiO2 assemblies, such as nc-TiO2 porous films and nc-TiO2 hierarchical structures, are now widely used in photocatalysis. The nc-TiO2 assemblies have quasi-disordered networks consisting of many tiny nanoparticles, so the charge transport within them can be studied by CTRW simulation. We considered the experimental facts that the holes can be quickly trapped and transferred to organic species just after photogeneration, and the electrons transfer to O2 slowly and accumulate in the conduction band of TiO2, which is believed to be the rate-limiting process of the photocatalysis under low light intensity and low organic concentration. Due to the existence of numerous traps, the electron transport within the nc-TiO2 assemblies follows a multi-trapping (MT) mechanism, which significantly limits the electron diffusion speed. The electrons need to undergo several steps of MT transport before transferring to oxygen, so it is highly important that the electron transport in nc-TiO2 networks is determined for standard photocatalytic reactions. Based on the MT transport model, the transient decays of photocurrents during the photocatalytic oxidation of formic acid were studied by CTRW simulation, and are in good accordance with experiments. The steady state photocatalysis was also simulated. The effects of organic concentration, light intensity, temperature, and nc-TiO2 crystallinity on the photocatalytic kinetics were investigated, and were also consistent with the experimental results. Due to the agreement between the simulation and the experiments for both the transient and the steady state photocatalysis, the MT charge transport should be an important mechanism that controls the kinetics of recombination and photocatalysis in nc-TiO2 assemblies. Also, our research provides a new methodology to study the photocatalytic dynamics from the random event viewpoint, which can be revised to investigate the kinetic processes of other kinds of material.

Thermodynamic and kinetic analysis of heterogeneous photocatalysis for semiconductor systems.

Since the report of the Honda-Fujishima effect, heterogeneous photocatalysis has attracted much attention around the world because of its potential energy and environmental applications. Although great progresses have been made in recent years, most were focused on preparing highly-active photocatalysts and investigating visible light utilization. In fact, we are still unclear on the thermodynamic and kinetic nature of photocatalysis to date, which sometimes leads to misunderstandings for experimental results. It is timely to give a review and discussion on the thermodynamics and kinetics of photocatalysis, so as to direct future researches. However, there is an absence of a detailed review on this topic until now. In this article, we tried to review and discuss the thermodynamics and kinetics of photocatalysis. We explained the thermodynamic driving force of photocatalysis, and distinguished the functions of light and heat in photocatalysis. The Langmuir-Hinshelwood kinetic model, the ˙OH oxidation mechanism, and the direct-indirect (D-I) kinetic model were reviewed and compared. Some applications of the D-I model to study photocatalytic kinetics were also discussed. The electron transport mode and its importance in photocatalysis were investigated. Finally, the intrinsic relation between the kinetics and the thermodynamics of photocatalytic reactions was discussed.

Investigation of electron behavior in Nano-TiO2 photocatalysis by using in situ open-circuit voltage and photoconductivity measurements.

The in situ open-circuit voltages (Voc ) and the in situ photoconductivities have been measured to study electron behavior in photocatalysis and its effect on the photocatalytic oxidation of methanol. It was observed that electron injection to the conduction band (CB) of TiO2 under light illumination during photocatalysis includes two sources: from the valence band (VB) of TiO2 and from the methanol molecule. The electron injection from methanol to TiO2 is slower than that directly from the VB, which indicates that the adsorption mode of methanol on the TiO2 surface can change between dark and illuminated states. The electron injection from methanol to the CB of TiO2 leads to the upshift of the Fermi level of electrons in TiO2 , which is the thermodynamic driving force of photocatalytic oxidation. It was also found that the charge state of nano-TiO2 is continuously changing during photocatalysis as electrons are injected from methanol to TiO2 . Combined with the apparent Langmuir-Hinshelwood kinetic model, the relation between photocatalytic kinetics and electrons in the TiO2 CB was developed and verified experimentally. The photocatalytic rate constant is the variation of the Fermi level with time, based on which a new method was developed to calculate the photocatalytic kinetic rate constant by monitoring the change of Voc with time during photocatalysis.

Grain Boundary Elimination via Recrystallization-Assisted Vapor Deposition for Efficient and Stable Perovskite Solar Cells and Modules.

Vapor deposition is a promising technology for the mass production of perovskite solar cells. However, the efficiencies of solar cells and modules based on vapor-deposited perovskites are significantly lower than those fabricated using the solution method. Emerging evidence suggests that large defects are generated during vapor deposition owing to a specific top-down crystallization mechanism. Herein, a hybrid vapor deposition method combined with solvent-assisted recrystallization for fabricating high-quality large-area perovskite films with low defect densities is presented. It is demonstrated that an intermediate phase can be formed at the grain boundaries, which induces the secondary growth of small grains into large ones. Consequently, perovskite films with substantially reduced grain boundaries and defect densities are fabricated. Results of temperature-dependent charge-carrier dynamics show that the proposed method successfully suppresses all recombination reactions. Champion efficiencies of 21.9% for small-area (0.16 cm2 ) cells and 19.9% for large-area (10.0 cm2 ) solar modules under AM 1.5 G irradiation are achieved. Moreover, the modules exhibit high operational stability, i.e., they retain >92% of their initial efficiencies after 200 h of continuous operation.

Metabolomics integrated with machine learning to discriminate the geographic origin of Rougui Wuyi rock tea.

The geographic origin of agri-food products contributes greatly to their quality and market value. Here, we developed a robust method combining metabolomics and machine learning (ML) to authenticate the geographic origin of Wuyi rock tea, a premium oolong tea. The volatiles of 333 tea samples (174 from the core region and 159 from the non-core region) were profiled using gas chromatography time-of-flight mass spectrometry and a series of ML algorithms were tested. Wuyi rock tea from the two regions featured distinct aroma profiles. Multilayer Perceptron achieved the best performance with an average accuracy of 92.7% on the training data using 176 volatile features. The model was benchmarked with two independent test sets, showing over 90% accuracy. Gradient Boosting algorithm yielded the best accuracy (89.6%) when using only 30 volatile features. The proposed methodology holds great promise for its broader applications in identifying the geographic origins of other valuable agri-food products.

Polymeric adsorption of methylene blue in TiO2 colloids-highly sensitive thermochromism and selective photocatalysis.

The polymeric adsorption of methylene blue (MB) on a TiO(2) surface is reported. The MB molecule on the TiO(2) surface mainly exists as the H-trimeric adsorption state, which results in the MB@TiO(2) polymeric sol. The trimeric adsorption leads to a remarkable "blueshift" of visible-light adsorption of MB. Electrostatic attraction is important for trimeric adsorption of MB on TiO(2) surfaces. The trimer-monomer equilibrium is highly sensitive on temperature changes, showing an interesting reversible thermochromism. The MB@TiO(2) polymeric sol can be photodegraded under UV illumination without destroying the equilibrium of trimer-monomer. Compared with anionic methyl orange, the TiO(2) colloid hydrosol shows highly selective photocatalysis of MB and other cationic dyes, including crystal violet, methylene green, and victoria blue B. The MB@TiO(2) polymeric sol is stable under visible-light illumination because interfacial transfer of electrons does not exist between MB and TiO(2).

Effect of Vacuum-Sealed Annealing and Ice-Water Quenching on the Structure and Photocatalytic Acetone Oxidations of Nano-TiO2 Materials.

In the current research, P25 TiO2 materials sealed in quartz vacuum tubes were subject to annealing and ice-water post-quenching, with the effects on TiO2 structures, morphology, and photocatalytic activity being studied. It is shown that the vacuum-sealed annealing can lead to a decrease in the crystallinity and temperature of anatase-to-rutile phase transition. A disorder layer is formed over TiO2 nanoparticles, and the TiO2 lattices are distorted between the disorder layer and crystalline core. The ice-water post-quenching almost has no effect on the crystalline structure and morphology of TiO2. It can be seen that the vacuum-sealed annealing can generate more defects, and the electrons are mainly localized at lattice Ti sites, as well as the percentage of bulk oxygen defects is also increased. Although further ice-water post-quenching can introduce more defects in TiO2, it does not affect the electron localization and defect distribution. The vacuum-sealed annealing process can increase the photocatalytic acetone oxidations of the anatase phase TiO2 to some extent, possibly because of the defect generation and Ti3+ site formation; the further ice-water quenching leads to a decrease in the photocatalytic activity because more defects are introduced.