Transplanting Gold Active Sites into Non-Precious-Metal Nanoclusters for Efficient CO2-to-CO Electroreduction.

Electrocatalytic CO2 reduction reaction (CO2RR) is greatly facilitated by Au surfaces. However, large fractions of underlying Au atoms are generally unused during the catalytic reaction, which limits mass activity. Herein, we report a strategy for preparing efficient electrocatalysts with high mass activities by the atomic-level transplantation of Au active sites into a Ni4 nanocluster (NC). While the Ni4 NC exclusively produces H2, the Au-transplanted NC selectively produces CO over H2. The origin of the contrasting selectivity observed for this NC is investigated by combining operando and theoretical studies, which reveal that while the Ni sites are almost completely blocked by the CO intermediate in both NCs, the Au sites act as active sites for CO2-to-CO electroreduction. The Au-transplanted NC exhibits a remarkable turnover frequency and mass activity for CO production (206 molCO/molNC/s and 25,228 A/gAu, respectively, at an overpotential of 0.32 V) and high durability toward the CO2RR over 25 h.

Visible-Light Activation of a Dissolved Organic Matter-TiO2 Complex Mediated via Ligand-to-Metal Charge Transfer.

Given the widespread use of TiO2, its release into aquatic systems and complexation with dissolved organic matter (DOM) are highly possible, making it important to understand how such interactions affect photocatalytic activity under visible light. Here, we show that humic acid/TiO2 complexes (HA/TiO2) exhibit photoactivity (without significant electron-hole activation) under visible light through ligand-to-metal charge transfer (LMCT). The observed visible-light activities for pollutant removal and bacterial inactivation are primarily linked to the generation of H2O2via the conduction band. By systematically considering molecular-scale interactions between TiO2 and organic functional groups in HA, we find a key role of phenolic groups in visible-light absorption and H2O2 photogeneration. The photochemical formation of H2O2 in river waters spiked with TiO2 is notably elevated above naturally occurring H2O2 generated from background organic constituents due to LMCT contribution. Our findings suggest that H2O2 generation by HA/TiO2 is related to the quantity and functional group chemistry of DOM, which provides chemical insights into photocatalytic activity and potential ecotoxicity of TiO2 in environmental and engineered systems.

Organometallic Iridium(III) Complex Sensitized Ternary Hybrid Photocatalyst for CO2 to CO Conversion.

A series of heteroleptic iridium(III) complexes functionalized with two phosphonic acid (-PO3 H2 ) groups (dfppy IrP, ppy IrP, btp IrP, and piq IrP) were prepared and anchored onto rhenium(I) catalyst (ReP)-loaded TiO2 particles (TiO2 /ReP) to build up a new IrP-sensitized TiO2 photocatalyst system (IrP/TiO2 /ReP). The photosensitizing behavior of the IrP series was examined within the IrP/TiO2 /ReP platform for the photocatalytic conversion of CO2 into CO. The four IrP-based ternary hybrids showed increased conversion activity and durability than that of the corresponding homo- (IrP+ReP) and heterogeneous (IrP+TiO2 /ReP) mixed systems. Among the four IrP/TiO2 /ReP photocatalysts, the low-energy-light (>500 nm) activated piq IrP immobilized ternary system (piq IrP/TiO2 /ReP) exhibited the most durable conversion activity, giving a turnover number of ≥730 for 170 h. A similar kinetic feature observed through time-resolved photoluminescence measurements of both btp IrP/TiO2 and TiO2 -free btp IrP films suggests that the net electron flow in the ternary hybrid proceeds dominantly through a reductive quenching mechanism, unlike the oxidative quenching route of typical dye/TiO2 -based photolysis.

Carbon Dioxide Dimer Radical Anion as Surface Intermediate of Photoinduced CO2 Reduction at Aqueous Cu and CdSe Nanoparticle Catalysts by Rapid-Scan FT-IR Spectroscopy.

Monitoring of visible light sensitized reduction of CO2 at Cu nanoparticles in aqueous solution by rapid-scan ATR FT-IR spectroscopy on the time scale of seconds allowed structural identification of a one-electron intermediate and demonstrated its kinetic relevancy for the first time. Isotopic labeling (12C: 1632, 1358, 1346 cm-1; 13C: 1588, 1326, 1316 cm-1) revealed a species of carbon dioxide dimer radical anion structure, most likely bound to the catalyst surface through carbon. Intermediacy of Cu-C(═O)OCO2- surface species is in agreement with a recently proposed mechanism for electrocatalytic CO2 reduction at Cu metal nanoparticles based on Tafel slope analysis. Spontaneous decrease of the intermediate after termination of the photosensitization pulse (Sn porphyrin excited at 405 nm) was accompanied by the growth of HCO3-. CO was produced as well, but sensitive detection required photolysis for tens of minutes. A direct kinetic link between a C2O4- surface intermediate and the CO product was also demonstrated for photocatalyzed CO2 reduction at aqueous CdSe nanoparticles, where first order growth of a Cd-C(═O)OCO2- species was accompanied by rise of CO (monitored by a fast Ni complex trap) and HCO3- showing a distinct induction period. The detection of the one-electron surface intermediate and confirmation of its catalytic relevancy was enabled by the delivery of electrons one-by-one by the photosensitization method. The observation of carbon dioxide dimer radical anion points to approaches for rate enhancements of heterogeneous CO2 reduction by creating catalytic environments that favor formation of this intermediate.

Active {001} Facet Exposed TiO2 Nanotubes Photocatalyst Filter for Volatile Organic Compounds Removal: From Material Development to Commercial Indoor Air Cleaner Application.

TiO2 nanotubes (TNT) have a highly ordered open structure that promotes the diffusion of dioxygen and substrates onto active sites and exhibit high durability against deactivation during the photocatalytic air purification. Herein, we synthesized {001} facet-exposed TiO2 nanotubes (001-TNT) using a new and simple method that can be easily scaled up, and tested them for the photocatalytic removal of volatile organic compounds (VOCs) in both a laboratory reactor and a commercial air cleaner. While the surface of TNT is mainly composed of {101} facet anatase, 001-TNT's outer surface was preferentially aligned with {001} facet anatase. The photocatalytic degradation activity of toluene on 001-TNT was at least twice as high as that of TNT. While the TNT experienced a gradual deactivation during successive cycles of photocatalytic degradation of toluene, the 001-TNT did not exhibit any sign of catalyst deactivation under the same test conditions. Under visible light irradiation, the 001-TNT showed degradation activity for acetaldehyde and formaldehyde, while the TNT did not exhibit any degradation activity for them. The 001-TNT filter was successfully scaled up and installed on a commercial air cleaner. The air cleaner equipped with the 001-TNT filters achieved an average VOCs removal efficiency of 72% (in 30 min of operation) in a 8-m3 test chamber, which satisfied the air cleaner standards protocol (Korea) to be the first photocatalytic air cleaner that passed this protocol.

Hierarchical Inorganic Assemblies for Artificial Photosynthesis.

Artificial photosynthesis is an attractive approach for renewable fuel generation because it offers the prospect of a technology suitable for deployment on highly abundant, non-arable land. Recent leaps forward in the development of efficient and durable light absorbers and catalysts for oxygen evolution and the growing attention to catalysts for carbon dioxide activation brings into focus the tasks of hierarchically integrating the components into assemblies for closing of the photosynthetic cycle. A particular challenge is the efficient coupling of the multi-electron processes of CO2 reduction and H2O oxidation. Among the most important requirements for a complete integrated system are catalytic rates that match the solar flux, efficient charge transport between the various components, and scalability of the photosynthetic assembly on the unprecedented scale of terawatts in order to have impact on fuel consumption. To address these challenges, we have developed a heterogeneous inorganic materials approach with molecularly precise control of light absorption and charge transport pathways. Oxo-bridged heterobinuclear units with metal-to-metal charge-transfer transitions absorbing deep in the visible act as single photon, single charge transfer pumps for driving multi-electron catalysts. A photodeposition method has been introduced for the spatially directed assembly of nanoparticle catalysts for selective coupling to the donor or acceptor metal of the light absorber. For CO2 reduction, a Cu oxide cluster is coupled to the Zr center of a ZrOCo light absorber, while coupling of an Ir nanoparticle catalyst for water oxidation to the Co donor affords closing of the photosynthetic cycle of CO2 conversion by H2O to CO and O2. Optical, vibrational, and X-ray spectroscopy provide detailed structural knowledge of the polynuclear assemblies. Time resolved visible and rapid-scan FT-IR studies reveal charge transfer mechanisms and transient surface intermediates under photocatalytic conditions for guiding performance improvements. Separation of the water oxidation and carbon dioxide reduction half reactions by a membrane is essential for efficient photoreduction of CO2 by H2O to liquid fuel products. A concept of a macroscale artificial photosystem consisting of arrays of Co oxide-silica core-shell nanotubes is introduced in which each tube operates as a complete, independent photosynthetic unit with built-in membrane separation. The ultrathin amorphous silica shell with embedded molecular wires functions as a proton conducting, molecule impermeable membrane. Photoelectrochemical and transient optical measurements confirm tight control of charge transport through the membrane by the orbital energetics of the wire molecules. Hierarchical arrangement of the components is accomplished by a combination of photodeposition, controlled anchoring, and atomic layer deposition methods.

Environmentally benign synthesis of CuInS2/ZnO heteronanorods: visible light activated photocatalysis of organic pollutant/bacteria and study of its mechanism.

Due to its high light absorption coefficient and appropriate bandgap, CuInS2 (CIS) has been receiving much attention as an absorber material for thin film solar cells and also as a visible light photocatalyst. Herein we present heterostructured CIS/ZnO nanorods (NRs) in an attempt to enhance light absorption and facilitate charge separation/transfer in the photocatalysis system. CIS nanoparticles (NPs) were directly deposited on ZnO nanorod arrays (NRAs) to fabricate heterostructured CIS/ZnO NRAs using an environmentally benign, non-hydrazine solution reaction. These heterostructured NRAs are immobilized on FTO glass, which has additional merits of recyclability and bias-applicability. The ideal type-II band structure of CIS/ZnO enables efficient charge separation/transfer, which is confirmed by PL (photoluminescence) decay measurements. Also, the 1D-ZnO NR structure facilitates fast charge transfer along with enhancing light absorption via light scattering. These synergistic effects improved the photocatalytic activity in both organic dye and bacteria decomposition. The photodecomposition efficiency was further enhanced with an aid of external bias. The underlying photocatalytic mechanism was also investigated through controlled experiments under various scavenging conditions. The results suggest that reactive oxygen species (ROS) formed by multistep reduction of O2 play a main role in photocatalysis, while hole-induced photodecomposition is relatively deactivated due to the band structure of the heterostructures of CIS/ZnO.

Coupling carbon dioxide reduction with water oxidation in nanoscale photocatalytic assemblies.

The reduction of carbon dioxide by water with sunlight in an artificial system offers an opportunity for utilizing non-arable land for generating renewable transportation fuels to replace fossil resources. Because of the very large scale required for the impact on fuel consumption, the scalability of artificial photosystems is of key importance. Closing the photosynthetic cycle of carbon dioxide reduction and water oxidation on the nanoscale addresses major barriers for scalability as well as high efficiency, such as resistance losses inherent to ion transport over macroscale distances, loss of charge and other efficiency degrading processes, or excessive need for the balance of system components, to mention a few. For the conversion of carbon dioxide to six-electron or even more highly reduced liquid fuel products, introduction of a proton conducting, gas impermeable separation membrane is critical. This article reviews recent progress in the development of light absorber-catalyst assemblies for the reduction and oxidation half reactions with focus on well defined polynuclear structures, and on novel approaches for optimizing electron transfer among the molecular or nanoparticulate components. Studies by time-resolved optical and infrared spectroscopy for the understanding of charge transfer processes between the chromophore and the catalyst, and of the mechanism of water oxidation at metal oxide nanocatalysts through direct observation of surface reaction intermediates are discussed. All-inorganic polynuclear units for reducing carbon dioxide by water at the nanoscale are introduced, and progress towards core-shell nanotube assemblies for completing the photosynthetic cycle under membrane separation is described.

Harnessing and storing visible light using a heterojunction of WO3 and CdS for sunlight-free catalysis.

CdS and WO3 (CdS/WO3) bilayer film electrodes are fabricated to harness solar visible light (λ > 420 nm) and store photogenerated electrons for possible use during periods of unavailable sunlight. The overall film thickness is approximately 50-60 µm, while the CdS underlayer is slightly thinner than WO3 owing to a packing effect. The energetics of CdS and WO3 determined by optical and electrochemical analyses enables cascaded electron transfer from CdS to WO3. The open circuit potential (EOCP) of CdS/WO3 under visible light (approximately -0.35 V vs. SCE) is nearly maintained even in the absence of light, with a marginal decrease (∼0.15 V) in ∼20 h of darkness. Neither CdS nor WO3 alone exhibits such behavior. The electron lifetimes (τ) of CdS and WO3 are each less than 100 s, whereas coupling of the two increases τ to ∼2500 s at the EOCP. In the absence of dissolved O2, τ further increases, suggesting that O2 is the primary electron acceptor. In spite of oxic conditions, CdS/WO3 is capable of continuously reducing Cr(6+) to Cr(3+) and Ag(+) to Ag(0) after removal of visible light. The number of utilized (i.e., stored) electrons in the reductions of Cr(6+) and Ag(+) are estimated to be ∼1.08 × 10(17) and ∼0.87 × 10(17), respectively. The primary role of CdS is to be a visible-light absorber in the 420-565 nm wavelength range, transferring the photogenerated electrons to WO3. The electrons stored in WO3 are gradually released to electron acceptors with suitable redox potentials.

Mechanistic Investigations of Water Oxidation by a Molecular Cobalt Oxide Analogue: Evidence for a Highly Oxidized Intermediate and Exclusive Terminal Oxo Participation.

Artificial photosynthesis (AP) promises to replace society's dependence on fossil energy resources via conversion of sunlight into sustainable, carbon-neutral fuels. However, large-scale AP implementation remains impeded by a dearth of cheap, efficient catalysts for the oxygen evolution reaction (OER). Cobalt oxide materials can catalyze the OER and are potentially scalable due to the abundance of cobalt in the Earth's crust; unfortunately, the activity of these materials is insufficient for practical AP implementation. Attempts to improve cobalt oxide's activity have been stymied by limited mechanistic understanding that stems from the inherent difficulty of characterizing structure and reactivity at surfaces of heterogeneous materials. While previous studies on cobalt oxide revealed the intermediacy of the unusual Co(IV) oxidation state, much remains unknown, including whether bridging or terminal oxo ligands form O2 and what the relevant oxidation states are. We have addressed these issues by employing a homogeneous model for cobalt oxide, the [Co(III)4] cubane (Co4O4(OAc)4py4, py = pyridine, OAc = acetate), that can be oxidized to the [Co(IV)Co(III)3] state. Upon addition of 1 equiv of sodium hydroxide, the [Co(III)4] cubane is regenerated with stoichiometric formation of O2. Oxygen isotopic labeling experiments demonstrate that the cubane core remains intact during this stoichiometric OER, implying that terminal oxo ligands are responsible for forming O2. The OER is also examined with stopped-flow UV-visible spectroscopy, and its kinetic behavior is modeled, to surprisingly reveal that O2 formation requires disproportionation of the [Co(IV)Co(III)3] state to generate an even higher oxidation state, formally [Co(V)Co(III)3] or [Co(IV)2Co(III)2]. The mechanistic understanding provided by these results should accelerate the development of OER catalysts leading to increasingly efficient AP systems.

Light induced carbon dioxide reduction by water at binuclear ZrOCo(II) unit coupled to Ir oxide nanocluster catalyst.

An all-inorganic polynuclear unit consisting of an oxo-bridged binuclear ZrOCo(II) group coupled to an iridium oxide nanocluster (IrO(x)) was assembled on an SBA-15 silica mesopore surface. A photodeposition method was developed that affords coupling of the IrO(x) water oxidation catalyst with the Co donor center. The approach consists of excitation of the ZrOCo(II) metal-to-metal charge-transfer (MMCT) chromophore with visible light in the presence of [Ir(acac)3] (acac: acetylacetonate) precursor followed by calcination under mild conditions, with each step monitored by optical and infrared spectroscopy. Illumination of the MMCT chromophore of the resulting ZrOCo(II)-IrO(x) units in the SBA-15 pores loaded with a mixture of (13)CO2 and H2O vapor resulted in the formation of (13)CO and O2 monitored by FT-IR and mass spectroscopy, respectively. Use of (18)O labeled water resulted in the formation of (18)O2 product. This is the first example of a closed photosynthetic cycle of carbon dioxide reduction by water using an all-inorganic polynuclear cluster featuring a molecularly defined light absorber. The observed activity implies successful competition of electron transfer between the IrO(x) catalyst cluster and the transient oxidized Co donor center with back electron transfer of the ZrOCo light absorber, and is further aided by the instant desorption of the CO and O2 product from the silica pores.

Inorganic core-shell assemblies for closing the artificial photosynthetic cycle.

Co oxide (Co(3)O(4)) nanotubes are shown to act as an efficient water oxidation catalyst when driven with a visible light sensitizer (pH 7). The nanotubes form the core of a Co(3)O(4)-SiO(2) core-shell nanotube design for separating the carbon dioxide photoreduction from the oxygen evolution reaction. Amorphous dense phase silica of a few nanometers depth is shown to conduct protons while blocking molecular oxygen. Organic molecular wires embedded in the silica shell provide controlled charge transport between the light absorber on one side and the Co(3)O(4) catalyst on the other side. Hence, the silica shell is suitable as a membrane of an assembly for closing the photosynthetic cycle on the nanometer scale under product separation.

Molecular-level understanding of the photocatalytic activity difference between anatase and rutile nanoparticles.

The generation of oxidants on illuminated photocatalysts and their participation in subsequent reactions are the main basis of the widely investigated photocatalytic processes for environmental remediation and selective oxidation. Here, the generation and the subsequent diffusion of (·)OH from the illuminated TiO2 surface to the solution bulk were directly observed using a single-molecule detection method and this molecular phenomenon could explain the different macroscopic behavior of anatase and rutile in photocatalysis. The mobile (·)OH is generated on anatase but not on rutile. Therefore, the photocatalytic oxidation on rutile is limited to adsorbed substrates whereas that on anatase is more facile and versatile owing to the presence of mobile (·)OH. The ability of anatase to generate mobile (·)OH is proposed as a previously unrecognized key factor that explains the common observations that anatase has higher activity than rutile for many photooxidative reactions.

Time-resolved spectroscopic investigation for the practical application of a photocatalytic air purifier.

The photocatalytic efficiency for removing volatile organic compounds (VOCs) is significantly influenced by operational parameters like humidity and flow velocity, exhibiting notable and inconsistent fluctuations in both lab-scale and large-scale demonstrations. In this study, operando spectroscopy and isotope analysis were employed to investigate the correlation between humidity levels and degradation of gaseous acetaldehyde using TiO2 photocatalysts, aiming to demonstrate the scaling-up of photocatalytic air purifier. It was observed that rate constants for the mineralization of acetaldehyde rapidly decreased by 30% as relative humidity increased from 25% to 80% in the flow system (with an air velocity, v = 0.78 m/s). However, batch system showed smaller change with only a 10% reduction of the rate constant. Humidity fluctuations were more pronounced under high-speed conditions and were amplified in air purifier (v = 3.8 m/s). Time-resolved operando spectroscopy using an 13C isotope of acetaldehyde revealed that humidity's distinct role in dark adsorption and photocatalytic reactions. Water was found to inhibit the formation of crotonaldehyde during aldol condensation reaction in dark condition. Moreover, water suppressed photocatalytic mineralization by inhibiting acetate oxidation to formate. These findings provide valuable insights for improving realistic air purification processes, underscoring the importance of identifying key intermediates and controlling humidity to enhance the selectivity of gaseous pollutant oxidation reactions.

Vitamin C-induced CO2 capture enables high-rate ethylene production in CO2 electroreduction.

High-rate production of multicarbon chemicals via the electrochemical CO2 reduction can be achieved by efficient CO2 mass transport. A key challenge for C-C coupling in high-current-density CO2 reduction is how to promote *CO formation and dimerization. Here, we report molecularly enhanced CO2-to-*CO conversion and *CO dimerization for high-rate ethylene production. Nanoconfinement of ascorbic acid by graphene quantum dots enables immobilization and redox reversibility of ascorbic acid in heterogeneous electrocatalysts. Cu nanowire with ascorbic acid nanoconfined by graphene quantum dots (cAA-CuNW) demonstrates high-rate ethylene production with a Faradaic efficiency of 60.7% and a partial current density of 539 mA/cm2, a 2.9-fold improvement over that of pristine CuNW. Furthermore, under low CO2 ratio of 33%, cAA-CuNW still exhibits efficient ethylene production with a Faradaic efficiency of 41.8%. We find that cAA-CuNW increases *CO coverage and optimizes the *CO binding mode ensemble between atop and bridge for efficient C-C coupling. A mechanistic study reveals that ascorbic acid can facilitate *CO formation and dimerization by favorable electron and proton transfer with strong hydrogen bonding.

Selective oxidative degradation of organic pollutants by singlet oxygen-mediated photosensitization: tin porphyrin versus C60 aminofullerene systems.

This study evaluates the potential application of tin porphyrin- and C(60) aminofullerene-derivatized silica (SnP/silica and aminoC(60)/silica) as (1)O(2) generating systems for photochemical degradation of organic pollutants. Photosensitized (1)O(2) production with SnP/silica, which was faster than with aminoC(60)/silica, effectively oxidized a variety of pharmaceuticals. Significant degradation of pharmaceuticals in the presence of the 400-nm UV cutoff filter corroborated visible light activation of both photosensitizers. Whereas the efficacy of aminoC(60)/silica for (1)O(2) production drastically decreased under irradiation with λ > 550 nm, Q-band absorption caused negligible loss of the photosensitizing activity of SnP/silica in the long wavelength region. Faster destruction of phenolates by SnP/silica and aminoC(60)/silica under alkaline pH conditions further implicated (1)O(2) involvement in the oxidative degradation. Direct charge transfer mediated by SnP, which was inferred from nanosecond laser flash photolysis, induced significant degradation of neutral phenols under high power light irradiation. Self-sensitized destruction caused gradual activity loss of SnP/silica in reuse tests unlike aminoC(60)/silica. The kinetic comparison of SnP/silica and TiO(2) photocatalyst in real wastewater effluents showed that photosensitized singlet oxygenation of pharmaceuticals was still efficiently achieved in the presence of background organic matters, while significant interference was observed for photocatalyzed oxidation involving non-selective OH radical.

Changes in levels of N-nitrosamine formed from amine-containing compounds during chloramination via photocatalytic pretreatment with immobilized TiO2: Effect of source water and pH.

We investigated the effectiveness of photocatalytic pretreatment (PCP) of precursors in minimizing the formation potentials (FPs) of carcinogenic nitrosamines, including N-nitrosodimethylamine (NDMA), N-nitrosodiethylamine (NDEA), and N-nitrosodiethanolamine (NDELA), during water chloramination. A steel mesh substrate with immobilized TiO2 was highly efficient at mitigating nitrosamine formation and removing targeted precursors such as ranitidine, nizatidine, trimebutine, triethanolamine, and metoclopramide. Compared to UVC/H2O2, PCP under UVA irradiation (intensity of 0.67 mW cm-2) was more effective for reducing nitrosamine-FPs during post-chloramination. However, the PCP efficacies varied with the water source, pretreatment pH, and irradiation time. For example, PCP of eutrophic water increased the NDMA-FPs, but produced notable reductions (up to 99%) for NDELA- and NDEA-FPs. Shorter irradiation times, up to 15 min, increased the NDELA-FP in triethanolamine, and the NDMA-FP in nizatidine and trimebutine. However, the nitrosamine-FP decreased by > 50% after PCP at a pH > 5.6, following irradiation for 120 min. Oxygen addition, N-de(m)ethylation, and N-dealkylation were responsible for decreasing nitrosamine-FPs via the destruction of key moieties; this has been elucidated by mass spectroscopy. This study suggests that PCP could be used as an alternative strategy for minimizing nitrosamine-FPs during water treatment.

Investigation of the AgCl Formation Mechanism on the Ag Wire Surface for the Fabrication of a Marine Low-Frequency-Electric-Field-Detection Ag/AgCl Sensor Electrode.

One of the most widely used electric field sensors for low-frequency electric field detection (LFEFD) in seawater uses the Ag/AgCl electrode. The surface structure of the electrode including AgCl layers plays a critical role in the electrode's electrochemical performance required for the sensor. In this study, the sequential AgCl formation process under the constant current was examined on the Ag wire in an electrode size for actual applications, and an optimal electrode surface structure was suggested for the LFEFD Ag/AgCl sensor. Upon mild anodization (0.2 mA/cm2) in 3.3 M KCl solution that permits us to follow the AgCl formation process manageably, Ag dissolution from the wire surface begins leaving cavities on the surface, with the accompanied growth of initial Ag grains. During this period, AgCl deposits in sizes of about several micrometers to 10 µm with crystal planes also form primarily along scratch lines on the wire surface, but in a partial scale. Then, with further anodization, the assumed thin AgCl deposits start to form, covering a large portion of the wire surface. They grow to become deposits in sizes of about several micrometers to 10 µm with no clear facet planes next to one another and are connected to form the network structure, representing the main developing mode of the AgCl deposits. While they cover all the surface, AgCl deposits also form on the surface of the already formed ones, making multiple AgCl layers. All these deposits develop through the nucleation process with a relatively high surface energy barrier, and their formation rate is solely controlled by the release rate of Ag+ from the wire, thus by the applied current magnitude. The Ag/AgCl electrode with a thick AgCl layer and many holes in the AgCl surface structure like microchannels is considered to work effectively for the LFEFD sensor in terms of both detection sensitivity and service lifetime.

Harnessing Waste Heat from Indoor lamps for Sustainable Thermocatalytic Mineralization of Acetaldehyde using Platinized TiO2.

This study demonstrates the first reported thermocatalytic oxidation of an indoor volatile organic compound (VOC), acetaldehyde, by harnessing the waste-heat energy from indoor light sources (e.g., halogen lamps) without additional energy inputs. With an optimal Pt-TiO2 catalyst, the designed catalyst-coated lampshade was successfully activated under waste-heat energy (∼120 °C) and achieved the complete mineralization of CH3CHO into CO2 (k = 0.02 min-1). The catalytic activity of Pt-TiO2 was extremely dependent on its preparation method which greatly influenced the characteristics (e.g., oxidation state and size) of Pt. The thermocatalytic oxidation mechanism of CH3CHO over Pt-TiO2 was investigated, which revealed that O2 and H2O sources play vital roles. Although Pt is an expensive noble metal, the thermocatalytic process on the Pt-TiO2-coated lampshade without additional energy, along with its outstanding activity, can offset the high material cost. The proposed strategy offers a sustainable and feasible method for the degradation of indoor VOCs.

Erosion-Driven Enamel Crystallite Growth Phenomenon at the Tooth Surface In Vitro.

The erosion of tooth enamel is a common oral disease. The erosion pattern and location and the effects of nanoscale chemical composition on the erosion susceptibility of enamel have been well documented. However, the enamel remineralization accompanied by erosion and its underlying physicochemical mechanisms still remain poorly understood. Here, using rat molars selected for its good relevancy to human teeth, we investigated the remineralization behavior of the outermost enamel surface at the nanoscale level during erosion in diluted hydrochloric acid solutions. While particles on the outermost enamel surface that represent the termination of crystallites protruding to the surface from the near-surface core eroded by acid-attack, the lateral-growth of the particles (i.e., the main remineralization picture of the surface enamel) occurred concurrently. Ionic analyses indicate that the particle growth is driven by the local increase in pH near the eroding enamel surface as a result of the combination of the PO43- and CO32- released from the enamel surface with H+. As the pH increases eventually to the equilibrium pH level (∼5.5), a local supersaturation of solute ions is induced, resulting in particle growth. A simple growth model based on the experimental results together with an assumption that the particle growth is a diffusional process suggests that the particle growth rate is controlled by the degree of supersaturation and accommodation site for solute ions, which are affected by the pH of solution eroding the enamel surface. The remineralization mechanism presented by our study can explain how the enamel on being acid-exposed or tooth decay progress by beverage or food can naturally remineralize in the oral cavity and how remineralization can foster different surface topology at the nanoscale, depending on the pH value of etchant before the dental filling material is applied.