Ascorbic Acid Induced the Improved Oxygen Vacancy Defects of Bi4O5Br2 and Its Application on Photoelectrochemical Detection of DNA Demethylase MBD2 with Improved Detection Sensitivity.

Oxygen vacancy defects (OVs) are one of the main strategies for nanomaterials modification to improve the photoactivity, but current methods for fabricating OVs are usually complicated and harsh. It is important to develop simple, rapid, safe, and mild methods to fabricate OVs. By studying the effects of different weak reducing agents, the concentration of the reducing agent and the reaction time on fabrication of OVs, it is found that L-ascorbic acid (AA) gently and rapidly induces the increase of OVs in Bi4O5Br2 at room temperature. The increased OVs not only improve the adsorption of visible light, but also enhance the photocurrent response. Based on this, the preparation of OVs in Bi4O5Br2 is employed to the development of a photoelectrochemical biosensor for the detection of DNA demethylase of methyl-CpG binding domain protein 2 (MBD2). The biosensor shows a wide linear range of 0.1-400 ng mL-1 and a detection limit as low as 0.03 ng mL-1 (3σ). In addition, the effect of plasticizers on MBD2 activity is evaluated using this sensor. This work not only provides a novel method to prepare OVs in bismuth rich materials, but also explores a new novel evaluation tool for studying the ecotoxicological effects of contaminants.

Layered sphere-shaped TiO2 capped with gold nanoparticles on structural defects and their catalysis of formaldehyde oxidation.

We describe here a one-step method for the synthesis of Au/TiO2 nanosphere materials, which were formed by layered deposition of multiple anatase TiO2 nanosheets. The Au nanoparticles were stabilized by structural defects in each TiO2 nanosheet, including crystal steps and edges, thereby fixing the Au-TiO2 perimeter interface. Reactant transfer occurred along the gaps between these TiO2 nanosheet layers and in contact with catalytically active sites at the Au-TiO2 interface. The doped Au induced the formation of oxygen vacancies in the Au-TiO2 interface. Such vacancies are essential for generating active oxygen species (*O(-)) on the TiO2 surface and Ti(3+) ions in bulk TiO2. These ions can then form Ti(3+)-O(-)-Ti(4+) species, which are known to enhance the catalytic activity of formaldehyde (HCHO) oxidation. These studies on structural and oxygen vacancy defects in Au/TiO2 samples provide a theoretical foundation for the catalytic mechanism of HCHO oxidation on oxide-supported Au materials.

Oxygen Vacancy Defect Enhanced NIR-II Photothermal Performance of BiOxCl Nanosheets for Combined Phototherapy of Cancer Guided by Multimodal Imaging.

Narrow photo-absorption range and low carrier utilization are significant barriers that restrict the antitumor efficiency of 2D bismuth oxyhalide (BiOX, X = Cl, Br, I) nanosheets (NSs). Introducing oxygen vacancy (OV) defects can expand the absorption range and improve carrier utilization, which are crucial but also challenging. In this study, a series of BiOxCl NSs with different OV defect concentrations (x = 1, 0.7, 0.5) is developed, which shows full spectrum absorption and strong absorption in the second near-infrared region (NIR-II). Density functional theory calculations are utilized to calculate the crystal structure and density states of BiOxCl, which confirm that part of the carriers is separated by OV enhanced internal electric field to improve carrier utilization. The carriers without redox reaction can be trapped in the OV, leading to great majority of photo-generated carriers promoting the photothermal performance. Triggered by single NIR-II (1064 nm), BiOxCl NSs' bidirectional efficient utilization of carriers achieves synchronously combined phototherapy, leading to enhanced tumor ablation and multimodal diagnostic in vitro and vivo. It is thus believed that this work provides an innovative strategy to design and construct nanoplatforms of indirect band gap semiconductors for clinical phototheranostics.

Pt single atoms and defect engineering of TiO2-nanosheet-assembled hierarchical spheres for efficient room-temperature HCHO oxidation.

Achieving high atomic utilization and low cost of desirable Pt/TiO2 catalysts is a major challenge for room temperature HCHO oxidation. Here, the strategy of anchoring stable Pt single atoms by abundant oxygen vacancies over TiO2-nanosheet-assembled hierarchical spheres (Pt1/TiO2-HS) was designed to eliminate HCHO. A superior HCHO oxidation activity and CO2 yield (∼100% CO2 yield) at relative humidity (RH) > 50% over Pt1/TiO2-HS is achieved for long-term run. We attribute the excellent HCHO oxidation performance to the stable isolated Pt single atoms anchored on the defective TiO2-HS surface. The Ptδ+ on the Pt1/TiO2-HS surface has a facile intense electron transfer with the support by forming Pt-O-Ti linkages, driving HCHO oxidation effectively. Further in situ HCHO-DRIFTS revealed that the dioxymethylene (DOM) and HCOOH/HCOO- intermediates were further degraded via active OH- and adsorbed oxygen on the Pt1/TiO2-HS surface, respectively. This work may pave the way for the next generation of advanced catalytic materials for high-efficiency catalytic HCHO oxidation at room temperature.

Selective detection of trace carbon monoxide at room temperature based on CuO nanosheets exposed to (111) crystal facets.

In recent years, carbon monoxide (CO) intoxication incidents occur frequently, and the sensitive detection of CO is particularly significant. At present, most reported carbon monoxide (CO) sensors meet the disadvantage of high working temperature. It is always a challenge to realize the sensitive detection of carbon monoxide at room temperature. In this study, CuO nanosheets exposed more (111) active crystal facets and oxygen vacancy defects were synthesized by a simple and environmentally friendly one-step hydrothermal method. The sensor has good comprehensive gas sensing performance, compared with other sensors that can detect CO at room temperature. The response value to 100 ppm CO at room temperature is as high as 39.6. In addition, it also has excellent selectivity, low detection limit (100 ppb), good reproducibility, moisture resistance and long-term stability (60 days). This excellent gas sensing performance is attributed to the special structural characteristics of 2D materials and the synergistic effect of more active crystal facets exposed on the crystal surface and oxygen vacancy defects. Therefore, it is expected to become a promising sensitive material for rapid and accurate detection of trace CO gas under low energy consumption, reduce the risk of poisoning, and then effectively protect human life safety.

SERS-active WO3-x thin films with tunable surface plasmon resonance induced by defects from thermal treatment.

A series of WO3-x thin films with defects were obtained by thermal treatments from laser irradiation and annealing, respectively. The corresponding tunability of localized surface plasmon resonance properties and the enhancement of Raman scattering intensity were realized due to the defects in the WO3-x thin films after thermal treatments. With the changes of either laser power or annealing temperature, the crystalline quality of WO3-x thin film was declined with a red shift of the surface plasmon resonance wavelength from 464 nm to 482 nm. The as-treated WO3-x film shows good uniformity and reproducibility in Surface-enhanced Raman spectroscopy measurement, the detection limit for dye methylene blue can reach 10-8 mol/L, and enhancement factor is 1.38 × 106. Furthermore, the simulation result of finite-difference time-domain showed a substantial agreement with experimental results.

Boosting Electrical Response toward Trace Volatile Organic Compounds Molecules via Pulsed Temperature Modulation of Pt Anchored WO3 Chemiresistor.

Insufficient limit of detection (LoD) toward volatile organic compounds (VOCs) hinders the promising applications of metal oxide chemiresistors in emerging air quality monitoring and/or breath analysis. There is an inherent limitation of widely adopted strategies of creating sensitive chemiresistors then operating at the optimized temperature via a continuous heating (CH) mode. Herein, a strategy combining Pt single atoms anchoring (chemical sensitization) with pulsed temperature modulation (PTM, physical sensitization) is proposed. Apart from generating abundant surface asymmetric oxygen vacancy (Pt-VO -W) active sites at pulsed high temperature (HT) stage, inward diffusion of trace target VOCs across the sensing layer at pulsed low temperature stage (driven by PTM induced concentration gradient), can greatly enhance the charge interaction probability between the generated surface active species and the surrounding VOCs, and thus offers a novel avenue on addressing the bottleneck issue of low LoD by PTM. Triggered by HT of 300 °C, the responses of Pt anchored WO3 chemiresistor to 1 ppm trimethylamine (TMA) and xylene can be drastically boosted from 1.9 (CH) to 6541.5 (PTM) and 1.5 (CH) to 1001.1 (PTM), respectively. And ultra-low theoretic LoD of 0.78 ppt (TMA) and 0.18 ppt (xylene) are successfully achieved, respectively.

Regulated Li2 S Deposition toward Rapid Kinetics Li-S Batteries by a Separator Modified by CeO2 -Decorated Porous Carbon Nanostructure.

Although the high-energy-density lithium sulfur (Li-S) battery has been considered one of the most promising next-generation energy storage technology, the practical applications have been plagued by the sluggish reaction kinetics and the shuttle effect of lithium polysulfides intermediates. Here, to address the above issues, the authors report a novel separator modified by CeO2 -decorated porous carbon nanostructure (CeO2 /KB/PP). Benefiting from the strong polar surface and large specific surface area, (CeO2 -doped Ketjen Black) delivers efficient chemical adsorption toward lithium polysulfides. Moreover, rich oxygen vacancies of CeO2 provide abundant active sites to expedite lithium polysulfides conversion and regulate deposition and nucleation of Li2 S. Taking advantage of these merits, the battery with the CeO2 /KB/PP separator exhibits remarkable electrochemical performance, including low-capacity decay of only 0.06% per cycle over 1000 cycles at 2 C and superior rate capability of 627 mAh g-1 at 3 C. Even with a high sulfur loading of 6.6 mg cm-2 , the battery can achieve a high areal capacity of 3.6 mAh cm-2 after 100 cycles. This work provides a new application of rare-earth-based materials to facilitate Li-S batteries.

Comprehension of the Synergistic Effect between m&t-BiVO4/TiO2-NTAs Nano-Heterostructures and Oxygen Vacancy for Elevated Charge Transfer and Enhanced Photoelectrochemical Performances.

Through the utilization of a facile procedure combined with anodization and hydrothermal synthesis, highly ordered alignment TiO2 nanotube arrays (TiO2-NTAs) were decorated with BiVO4 with distinctive crystallization phases of monoclinic scheelite (m-BiVO4) and tetragonal zircon (t-BiVO4), favorably constructing different molar ratios and concentrations of oxygen vacancies (Vo) for m&t-BiVO4/TiO2-NTAs heterostructured nanohybrids. Simultaneously, the m&t-BiVO4/TiO2-NTAs nanocomposites significantly promoted photoelectrochemical (PEC) activity, tested under UV-visible light irradiation, through photocurrent density testing and electrochemical impedance spectra, which were derived from the positive synergistic effect between nanohetero-interfaces and Vo defects induced energetic charge transfer (CT). In addition, a proposed self-consistent interfacial CT mechanism and a convincing quantitative dynamic process (i.e., rate constant of CT) for m&t-BiVO4/TiO2-NTAs nanoheterojunctions are supported by time-resolved photoluminescence and nanosecond time-resolved transient photoluminescence spectra, respectively. Based on the scheme, the m&t-BiVO4/TiO2-NTAs-10 nanohybrids exhibited a photodegradation rate of 97% toward degradation of methyl orange irradiated by UV-visible light, 1.14- and 1.04-fold that of m&t-BiVO4/TiO2-NTAs-5 and m&t-BiVO4/TiO2-NTAs-20, respectively. Furthermore, the m&t-BiVO4/TiO2-NTAs-10 nanohybrids showed excellent PEC biosensing performance with a detection limit of 2.6 µM and a sensitivity of 960 mA cm-2 M-1 for the detection of glutathione. Additionally, the gas-sensing performance of m&t-BiVO4/TiO2-NTAs-10 is distinctly superior to that of m&t-BiVO4/TiO2-NTAs-5 and m&t-BiVO4/TiO2-NTAs-20 in terms of sensitivity and response speed.

Continuous flow scale-up of biofunctionalized defective ZnO quantum dots: A safer inorganic ingredient for skin UV protection.

The versatility of ZnO quantum dots (QDs) exhibiting size-tunable visible photoluminescence has propelled them to the forefront of leading-edge innovations in healthcare. At the nano-bio interface, enhancing the singly-ionized oxygen vacancy defects (VO•) through holistic, sustainable synthesis protocols driven by the synergistic influence of QDs' nucleation-growth kinetics has implications on their bioactivity, physiochemical, and optical performance. Recently, robust continuous flow platforms have transcended the conventional batch reactors by alleviating the concerns of "hot-spot" formation due to inhomogeneous heat distribution, acute energy consumption, poor quality, and yield. However, complexities exist in translating batch chemistries into flow processes. Here, a unique, rationally designed continuous flow synthesis of luminescent defect-engineered ZnO QDs (E-QDs) via helical-reactor assembly that can adequately synthesize on a large scale is reported. The crux of this lies in the amalgamation of "green chemistry" and flow synthesis, which results in Lamer-mechanism mediated monodispersed E-QDs demonstrating high photoluminescence quantum yield (PLQY) of 89% under an accurately regulated synthesis environment. Process intensification corroborated that the bio-stable E-QDs manifested admirable photostability, broad-spectrum UV-shielding (400-250 nm), colloidal stability, in vitro biocompatibility against L929 and HaCaT cells, and antioxidant activity. These attributes were better compared to the commercial ZnO nanoparticles (ZnOC-NPs) used for skin UV protection. Delving deeper, the main drivers for the high density of intrinsic VO• formation (Iv/Io∼42.5) were revealed to be the reactor's hydrodynamic performance and the improvised heating rate (2.5°C/sec). Hence, these E-QDs have potential as a new, safe, and economical multifunctional active ingredient for skin UV protection and antioxidants for treating ROS-mediated disorders. STATEMENT OF SIGNIFICANCE: UV filters exhibiting questionable UV-attenuation efficacy and phototoxicity are significant impediments to the healthcare industry emphasizing skin cancer prevention. Although least explored, VO•-governed aberrant photoactive, biological, and surface-reactive qualities of engineered ZnO QDs (E-QDs) have created ample room to investigate these hallmarks for skin UV protection. However, the bottlenecks in stereotypical ZnO QDs production confined by inefficient process control are annihilated by continuous flow strategies. Herein, the high-throughput continuous flow helical reactor assembly was designed and fabricated to successfully showcase optimized transport properties, reproducibility, yield, and quality E-QDs. Anticipating a skyrocketing demand for E-QDs as bioactive-sunscreen components, the comprehensive investigation has demonstrated unprecedented biofunctionality and ROS-scavenging behaviour, even upon UVR exposure, contrary to the traditional nanoparticulate ZnO UV filters.

Enriching Oxygen Vacancy Defects via Ag-O-Mn Bonds for Enhanced Diffusion Kinetics of δ-MnO2 in Zinc-Ion Batteries.

Aqueous zinc-ion batteries (ZIBs) have received great attention due to their environmental friendliness and high safety. However, cathode materials with slow diffusion dynamics and dissolution in aqueous electrolytes hindered their further application. To address these issues, in this work, a MnO2-2 cathode doped with 1.12 wt % Ag was prepared, and after 1000 cycles of charge/discharge at 1 A·g-1, the capacity remained at 114 mA·h·g-1 (only 57.7 mA·h·g-1 for pristine MnO2). Cyclic voltammetry (CV), the galvanostatic intermittent titration technique (GITT), the electrochemical quartz crystal microbalance (EQCM) method, and density functional theory (DFT) calculation on pristine δ-MnO2 and MnO2-2 also proved the superior performance of MnO2-2. More investigation disclosed that its superior performance is attributed to the improved diffusion kinetics of the cathode brought by the enriched oxygen vacancy defects due to the formation of Ag-O-Mn bonds. Meanwhile, the kinetic mechanism of the Zn/MnO2-2 cell can be described as a reversible process of the dissolution/precipitation of the ZHS phase and consequent insertion/extraction of Zn2+ and H3O+. Herein, the primary issues of ZIB cathode materials have been addressed and solved to a certain extent. More importantly, such a modification in the design of the advanced manganese-based aqueous ZIB cathode materials can provide further insight and facilitate the development and application of this large-scale energy storage system in the near future.

Charge-Transfer Induced by the Oxygen Vacancy Defects in the Ag/MoO3 Composite System.

In this paper, an Ag/MoO3 composite system was cosputtered by Ar plasma bombardment on a polystyrene (PS) colloidal microsphere array. The MoO3 formed by this method contained abundant oxygen vacancy defects, which provided a channel for charge transfer in the system and compensated for the wide band gap of MoO3. Various characterization methods strongly demonstrated the existence of oxygen vacancy defects and detected the properties of oxygen vacancies. 4-Aminothiophenol (p-aminothiophenol, PATP) was used as a candidate surface-enhanced Raman scattering (SERS) probe molecule to evaluate the contribution of the oxygen vacancy defects in the Ag/MoO3 composite system. Interestingly, oxygen vacancy defects are a kind of charge channel, and their powerful effect is fully reflected in their SERS spectra. Increasing the number of charge channels and increasing the utilization rate of the channels caused the frequency of SERS characteristic peaks to shift. This interesting phenomenon opens up a new horizon for the study of SERS in oxygen-containing semiconductors and provides a powerful reference for the study of PATP.

Oxygen Defect Hydrated Vanadium Dioxide/Graphene as a Superior Cathode for Aqueous Zn Batteries.

Zinc ion batteries have become a new type of energy storage device because of the low cost and high safety. Among the various cathode materials, vanadium-oxygen compounds stand out due to their high theoretical capacity and variable chemistry valence state. Here, we construct a 3D spongy hydrated vanadium dioxide composite (Od-HVO/rG) with abundant oxygen vacancy defects and graphene modifications. Thanks to the stable structure and abundant active sites, Od-HVO/rG exhibits superior electrochemical properties. In aqueous electrolyte, the Od-HVO/rG cathode provides high initial charging capacity (428.6 mAh/g at 0.1 A/g), impressive rate performance (186 mAh/g even at 20 A/g), and cycling stability, which can still maintain 197.5 mAh/g after 2000 cycles at 10 A/g. Also, the superior specific energy of 245.3 Wh/kg and specific power of 14142.7 W/kg are achieved. In addition, MXene/Od-HVO/rG cathode materials are prepared and PAM/ZnSO4 hydrogel electrolytes are applied to assemble flexible soft pack quasi-solid-state zinc ion batteries, which also exhibit excellent flexibility and cycling stability (206.6 mAh/g after 2000 cycles). This work lays the foundation for advances in rechargeable aqueous zinc ion batteries, while revealing the potential for practical applications of flexible energy storage devices.

Improved osteogenesis and angiogenesis of theranostic ions doped calcium phosphates (CaPs) by a simple surface treatment process: A state-of-the-art study.

Surface treatment of biomaterials could enable reliable and quick cellular responses and accelerate the healing of the host tissue. Here, a series of calcium phosphates (CaPs) were surface treated by hydrogen peroxide (H2O2) and the treatment effects were physicochemically and biologically evaluated. For this aim, as-synthesized CaPs doped with strontium (Sr2+), iron (Fe2+), silicon (Si4+), and titanium (Ti4+) ions were sonicated in H2O2 media. The results showed that the specific surface area and zeta potential values of the surface-treated CaPs were increased by ~50% and 25%, respectively. Moreover, the particle size and the band-gap (Eg) values of the surface-treated CaPs were decreased by ~25% and ~2-10%, respectively. The concentration of oxygen vacancies was increased in the surface-treated samples, which was confirmed by the result of ultraviolet (UV), photoluminescence (PL), Commission Internationale de l'éclairage (CIE 1931), and X-ray photoelectron spectroscopy (XPS) analyses. In vitro cellular assessments of surface-treated CaPs exhibited an improvement in cytocompatibility, reactive oxygen species generation (ROS) capacity, bone nodule formation, and the migration of cells up to ~8%, 20%, 35%, and 13%, respectively. Based on the obtained data, it can be stated that improved physicochemical properties of H2O2-treated CaPs could increase the ROS generation and subsequently enhance the biological activities. In summary, the results demonstrate the notable effect of the H2O2 surface treatment method on improving surface properties and biological performance of CaPs.

Visible light photocatalysis of amorphous Cl-Ta2O5-x microspheres for stabilized hydrogen generation.

Harvesting broad spectral absorption and visible light photocatalysis of ultrawide bandgap semiconductors are one of most significative topics in the solar energy conversion and utilization fields. In this work, amorphous Cl-Ta2O5-x microspheres were prepared by facile solvothermal method for stabilized visible light photocatalytic hydrogen generation. The acetone absorbed on the interfaces of Ta2O5 nanoparticles induced the formation of oxygen vacancies, enhanced visible light absorption, and formation of Ta2O5-x microspheres with preferred orientations as well as Cl doping. The Cl-Ta2O5-x microspheres showed typical amorphous characteristics and obvious visible light absorption in comparison to those of commercial Ta2O5. More importantly, the prepared Cl-Ta2O5-x microspheres also showed stabilized visible light photocatalytic hydrogen generation performance in the spectral regions of 400 nm ≤ λ ≤ 600 nm mainly because of the introduction of oxygen vacancy defects and Cl doping, which might significantly expand the application of tantalum oxide semiconductors in the broad spectral photocatalytic water splitting.

Oxygen Vacancy Defect-Induced Activity Enhancement of Gd Doping Magnetic Nanocluster for Oxygen Supplying Cancer Theranostics.

This work finds that Fe3O4 nanoclusters can rearrange by Gd doping and then self-assemble to a hollow magnetic nanocluster (HMNC), providing larger magnetic moments to obtain an excellent MRI capability and increasing the number of oxygen vacancies in HMNC. The hollow structure makes platinum(IV) prodrugs effectively load into HMNC. Second, plenty of oxygen vacancy defects can capture oxygen molecules, enhance the catalytic activity of HMNC, and then promote intracellular ROS generation. On the basis of this, a targeting iRGD-labeled HMNC nanosystem (iHMNCPt-O2) is developed through loading oxygen molecules and platinum(IV) prodrugs for chemo- and chemodynamic therapy of cancer. This nanosystem shows an excellent response ability to weak acid and GSH, which can cause a series of cascade reactions in a cell. These cascade reactions are dramatically enhanced at the intracellular ROS level, cause mitochondria and DNA damage, and then induce cancer cell death. Besides, systemic delivery of iHMNCPt-O2 significantly enhanced the MRI contrast signal of tumors and improved the quality of MR images, accurately diagnosing tumors. Therefore, this work provides a novel method for accelerating the Fenton-like reaction and enhancing the MRI capability and fabricates a promising "all-in-one" system to overwhelm the problems of cancer theranostic.

Suppression of Oxygen Vacancy Defects in sALD-ZnO Films Annealed in Different Conditions.

Zinc oxide (ZnO) has drawn much attention due to its excellent optical and electrical properties. In this study, ZnO film was prepared by a high-deposition-rate spatial atomic layer deposition (ALD) and subjected to a post-annealing process to suppress the intrinsic defects and improve the crystallinity and film properties. The results show that the film thickness increases with annealing temperature owing to the increment of oxide layer caused by the suppression of oxygen vacancy defects as indicated by the X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) spectra. The film transmittance is seldom influenced by annealing. The refractive index increases with annealing temperature at 300-700 °C, possibly due to higher density and crystallinity of the film. The band gap decreases after annealing, which should be ascribed to the decrease in carrier concentration according to Burstein-Moss model. The carrier concentration decreases with increasing annealing temperature at 300-700 °C since the oxygen vacancy defects are suppressed, then it increases at 800 °C possibly due to the out-diffusion of oxygen atoms from the film. Meanwhile, the carrier mobility increases with temperature due to higher crystallinity and larger crystallite size. The film resistivity increases at 300-700 °C then decreases at 800 °C, which should be ascribed primarily to the variation of carrier concentration.

Predicting NOx Catalysis by Quantifying Ce3+ from Surface and Lattice Oxygen.

Our work introduces a novel technique based on the magnetic response of Ce3+ and molecular oxygen adsorbed on the surface of nanoceria and ceria-based catalysts that quantifies the number and type of defects and demonstrates that this information is the missing link that finally enables predictive design of NOx catalysis in ceria-based systems. The new insights into ceria catalysis are enabled by quantifying the above for different ceria nanoparticle shapes (i.e., surface terminations) and O2 partial pressure. We used ceria nanorods, cubes, and spheres and evaluated them for catalytic reduction of NO by CO. We then demonstrated the quantitative prediction of the reactivity of nanomaterials via their magnetism in different atmospheric environments. We find that the observed enhancement of reactivity for ceria nanocubes and nanorods is not directly due to improved reactivity on those surface terminations but rather due to the increased ease of generating lattice defects in these materials. Finally, we demonstrate that the method is equally applicable to highly topical and industrially relevant ceria mixed oxides, using nanoscale alumina-supported ceria as a representative case-a most ill-defined catalyst. Because the total oxide surface is a mixture of active ceria and inactive support and ceria is not likely present as crystallographically well-defined phases, reactivity does not easily scale with surface area or a surface termination. The key parameter to design efficient NO reduction in ceria-based catalysts is knowing and controlling the surface localized excess Ce3+ ion areal density.