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Water-participation matters: the photo-induced single-proton/single-electron transfer pathway on TiO2 nanoparticles can be significantly switched from stepwise PT/ET to one-step CPET by adsorbed water molecules.

Epoxides are significant intermediates for the manufacture of pharmaceuticals and epoxy resins. In this study, we develop a Br−/BrO− mediated photoelectrochemical epoxidation system on α-Fe2O3. High selectivity (up to >99%) and faradaic efficiency (up to 82 ± 4%) for the epoxidation of a wide range of alkenes are achieved, with water as oxygen source, which are far beyond the most reported electrochemical and photoelectrochemical epoxidation performances. Further, we can verify that the epoxidation reaction is mediated by Br−/BrO− route, in which Br− is oxidized non-radically to BrO− by an oxygen atom transfer pathway on α-Fe2O3, and the formed BrO− in turn transfers its oxygen atom to the alkenes. The non-radical mediated characteristic and the favorable thermodynamics of the oxygen atom transfer process make the epoxidation reactions very efficient. We believe that this photoelectrochemical Br−/BrO−-mediated epoxidation provides a promising strategy for value-added production of epoxides and hydrogen.

Characteristic emerging pollutants at low concentration have raised much attention for causing a bottleneck in water remediation, especially in complex water matrices where high concentration of interferents coexist. In the future, tailored treatment methods are therefore of increasing significance for accurate removal of target pollutants in different water matrices. This critical review focuses on the overall strategies for accurately removing highly toxic emerging pollutants in the presence of typical interferents. The main difficulties hindering the improvement of selectivity in complex matrices are analyzed, implying that it is difficult to adopt a universal approach for multiple targets and water substrates. Selective methods based on assorted principles are proposed aiming to improve the anti-interference ability. Thus, typical approaches and fundamentals to achieve selectivity are subsequently summarized including their mechanism, superiority and inferior position, application scope, improvement method and the bottlenecks. The results show that different methods may be applicable to certain conditions and target pollutants. To better understand the mechanism of each selective method and further select the appropriate method, advanced methods for qualitative and quantitative characterization of selectivity are presented. The processes of adsorption, interaction, electron transfer, and bond breaking are discussed. Some comparable selective quantitative methods are helpful for promoting the development of related fields. The research framework of selectivity removal and its fundamentals are established. Presently, although continuous advances and remarkable achievements have been attained in the selective removal of characteristic organic pollutants, there are still various substantial challenges and opportunities. It is hopeful to inspire the researches on the new generation of water and wastewater treatment technology, which can selectively and preferentially treat characteristic pollutants, and establish a reliable research framework to lead the direction of environmental science.

Herein, we fabricated a π-π stacking hybrid photocatalyst by combining two two-dimensional (2D) materials: g-C3N4 and a Cu-porphyrin metal-organic framework (MOF). After an aerobic photocatalytic pretreatment, this hybrid catalyst exhibited an unprecedented ability to photocatalytically reduce CO2 to CO and CH4 under the typical level (20%) of O2 in the air. Intriguingly, the presence of O2 did not suppress CO2 reduction; instead, a fivefold increase compared with that in the absence of O2 was observed. Structural analysis indicated that during aerobic pretreatment, the Cu node in the 2D-MOF moiety was hydroxylated by the hydroxyl generated from the reduction of O2. Then the formed hydroxylated Cu node maintained its structure during aerobic CO2 reduction, whereas it underwent structural alteration and was reductively devitalized in the absence of O2. Theoretical calculations further demonstrated that CO2 reduction, instead of O2 reduction, occurred preferentially on the hydroxylated Cu node.

Both β- and γ- hydroxyketone structures are important units in biologically active molecules, synthetic drugs and fine chemicals. Although there are some routes available for their manufacture from pre-functionalized groups on one or two matrix molecule(s), the approaches to simply and simultaneously deposit two oxygen atoms from dioxygen into two specific C(sp3) positions of pure saturated hydrocarbons have rarely succeeded because they are involved in the targeted activation of three inert C-H σ bonds all at once. Here, we show that a TiO2-CH3CN photocatalytic suspension system enables the insertion of dioxygen into one C(sp3)-C(sp3) bond of strained cycloparaffin derivatives, by which difunctionalized hydroxyketone products are obtained in a one-pot reaction. With the cleavage event to release strain as the directional driving force, as-designed photocatalytic reaction systems show 21 examples of β-hydroxyketone products with 31%–76% isolated yields for three-membered ring derivatives and 5 examples of γ-hydroxyketone products with 30%–63% isolated yields for four-membered ring substrates. 18O isotopic labeling experiments using 18O2, Ti18O2 and intentionally added H218O, respectively, indicated that both oxygen atoms of hydroxyketone products were exclusively from dioxygen, suggesting a previously unknown H+/TiO2-e− catalyzed arrangement pathway of the hydroperoxide intermediate to convert dioxygen into hydroxyketone units.

Constructing heterostructures have been demonstrated as an ideal strategy for boosting charge separation on plasmonic photocatalysts, but the detailed interface charge transfer mechanism remains elusive. Herein, that authors fabricate plasmonic Au and metal-organic frameworks (MOFs, NH

Achieving CO2 reduction with H2O on metal photocatalysts and understanding the corresponding mechanisms at the molecular level are challenging. Herein, we report that quantum-sized Au nanoparticles can photocatalytically reduce CO2 to CO with the help of H2O by electron-hole pairs mainly originating from interband transitions. Notably, the Au photocatalyst shows a CO production rate of 4.73 mmol g−1 h−1 (~100% selectivity), ~2.5 times the rate during CO2 reduction with H2 under the same experimental conditions, under low-intensity irradiation at 420 nm. Theoretical and experimental studies reveal that the increased activity is induced by surface Au–O species formed from H2O decomposition, which synchronously optimizes the rate-determining steps in the CO2 reduction and H2O oxidation reactions, lowers the energy barriers for the *CO desorption and *OOH formation, and facilitates CO and O2 production. Our findings provide an in-depth mechanistic understanding for designing active metal photocatalysts for efficient CO2 reduction with H2O.

Light-driven dual catalysis that combines photosensitizers and transition-metal complexes has become a powerful approach for diverse cross-coupling reactions. Heterogeneous photocatalysts recently ...

Sulfate, as a major component of aerosol particles, greatly contributes to haze formation and affects global climate change. Although formation pathways of sulfate aerosols from the conversion of S...

Both Fe(III) and fatty acids are ubiquitous and important species in environmental waters. Because they are amphipathic, many fatty acids are surface active and prone to enrichment at the air-water interface. Here, we report that by using nonanoic acid (NA) as a model fatty acid, coexisting Fe(III), even at concentrations as low as 1 μM, markedly enhanced the photochemical release of NA-derived volatile organic compounds (VOCs) such as octanal and octane into the air. Further studies indicated that the surface-enriched fatty acids dramatically increase the local concentration of Fe(III) at the water surface, which enables Fe(III)-mediated photochemical reactions to take place at the air-water interface, and the VOCs facilely produced by fatty acid photooxidation can then be released into the air. Moreover, the product distribution in the Fe(III)-mediated reactions was largely different from that in other photochemical systems, and a mechanism based on photochemical decarboxylation is proposed. Considering that the coexistence of fatty acids and Fe(III) in the environment is common, the enhanced photochemical release of VOCs by surface-enriched fatty acids and Fe(III) may be an important channel for the atmospheric emission of VOCs, which are known to play an essential role in the formation of ozone and secondary organic aerosols.

Optimizing kinetic barriers of ammonia synthesis to reduce the energy intensity has recently attracted significant research interest. The motivation for the research is to discover means by which a...

Fenton reactions that activate H2O2 by using Fe2+ have emerged as a hot topic in environmental remediation. The sluggish regeneration of the active Fe2+ from Fe3+ remains the key limitation. As recently reported in Angewandte Chemie, Xing and co-workers have developed a MoS2-based heterogeneous co-catalyst that can significantly overcome this limitation and improve the overall efficiency.

The active nitrogen species (HONO, NO, and NO2) have important impacts on the atmospheric oxidative capacity and the transformation of many atmospheric species. In this study, a fast photochemical renoxification rate of adsorbed HNO3/NO3- to active nitrogen species (HONO, NO, and NO2) was detected on real urban PM2.5, and sulfate was found to play a key role in this process. Different from the reported direct photolysis pathway, the photochemical reaction of HNO3/NO3- on PM2.5 is dominated by a photosensitizing mechanism. Acidic protons are proved to be essential for this pathway. The role of sulfate, because of the nonvolatility of its conjugated acid, is to conserve the necessary acidic protons when interacting with HNO3 and thus maintain its photoreactivity. This work implies that sulfate will have important implications in atmospheric nitrogen cycling by accelerating the release of nitrogen oxides from photochemical renoxification of HNO3/NO3- adsorbed on ambient particulates and thus can cause major environmental problems.

Identifying the active catalytic centers on catalyst surface is significant for exploring the catalytic reaction mechanism and further guiding the synthesis of high-performance catalysts. However, it remains a challange in developing the site-specific technology for the identification of the active catalytic centers. Herein, in-situ infrared spectroscopy of adsorbed CO, photocatalytic hydrogen evolution reaction (HER) test and theoretical simulation were used to distinguish and quantify the different surface sites and their H2-production catalytic activity on TiO2-supported Pt nanoparticles (PtNPs). Two different types of surface Pt sites, tip Pt (Pttip) and edge/terrace Ptedge/terrace, on TiO2-supported Pt nanoparticles (PtNPs) were identified. The photocatalytic H2-production activity of TiO2-supported PtNPs shows a linear functional relationship with the number of Pttip sites. However, the number of Ptedge/terrace sites produced little effect on the activity of TiO2-supported PtNPs. First-principle simulations confirmed that H2-evolution at the Pttip sites owns a lower energy barrier than that at Ptedge/terrace. This findings would be helpful for the fabrication of high-performance Pt catalysts.

The reductive reactions driven by photo-generated electrons on photocatalysts were generally considered to be irrelevant to the employed hole-scavengers. Herein, we report an unexpected dependence of photocatalytic debromination of decabromodiphenyl ether (BDE 209) on the hole-scavengers catalyzed by amine-functionalized MIL-125(Ti). It was found that the debromination only occurred when triethanolamine, rather than the conventional alcohols, was used as the hole-scavenger. Further low-temperature ESR experiments indicate that triethanolamine participates in the formation of the active catalytic Ti (Ⅲ) species, which shuttle the electron to BDE 209, producing reductive debromination products.

Summary Artificial ammonia synthesis (Haber-Bosch process) is a prototypical exothermic reaction of maximum catalytic yield restricted by the unbreakable equilibrium law. This is because bottlenecked N2 dissociation necessitates high temperature, but high temperature reversely shifts the thermal equilibrium toward NH3 decomposition. To surmount this equilibrium limit, here, we propose a new scenario of dual-temperature-zone catalysis. Powered by sunlight, the apparent temperature of TiO2-xHy/Fe hybrid reaches 495°C but with local temperature difference up to 137°C between the hot zone (Fe) and “cooling” zone (TiO2-xHy) owing to the plasmonic local heating effect. The hot Fe bearing hot carriers efficiently dissociates N2, while working-in-tandem TiO2-xHy well accommodates spilled-over N from Fe via successive hydrogenation, prominently mitigating the reverse equilibrium shift and thus delivering record NH3 concentrations of 1,939 (1 atm) and 19,620 ppm (10 atm) at 495°C, 1.55 and 1.57 times the theoretical equilibrium limits of 1,249 and 12,459 ppm, respectively.

The controlled formation of complex and functional 1-, 2-, and 3D hierarchical assemblies from molecular building blocks represents a key current challenge. Herein, we report the use of a seeded growth approach for a series of perylenediimide-based molecules (PDIs 1-4) to access otherwise inaccessible self-assembly pathways that yield complex hierarchical structures. The key to the new approach is to use hetero-seeds which possess a different composition and morphology from that of the molecular building block. For example, a nanotube seed (from PDI 3) and a microribbon seed (from PDI 4) were found to initiate different self-assembly pathways for PDI 1, which normally assembles to yield nanocoils. This led to the formation of unprecedented 3D scroll-like and scarf-like hierarchical nanostructures, respectively. Also, the hetero-seeds from PDI 3 initiate hidden self-assembly pathways of PDI 2 to generate 1D tubular heterojunctions. Significantly, this new strategy offers new opportunities to create emergent and functional hierarchical and complex structures from small molecule precursors.

The photochemical aging of soot in the aqueous phase could have an important influence on water environments such as fog water and wet aerosols in the atmosphere, as well as lakes and oceans. In this study, we systematically investigated the photochemistry of soot in the aqueous phase. Soot releases dissolved black carbon into the aqueous phase during photoreactions, which is attributed to the phototransformation of the nonpolar unsaturated C-H species in soot to polar carbonyl-containing species. More importantly, we found that soot suspensions, particularly those of the dissolved part of soot, were effective photosensitizers for the generation of singlet oxygen (1O2). The 1O2 apparent quantum yield of the dissolved part reached 33 ± 2% under 377 nm irradiation, which is an order of magnitude higher than those of most types of well-studied dissolved organic matter in water. As a result, soot could impact the environmental fate of coexisting organic contaminants, such as the photodegradation of bisphenol A. This study will not only give insight into the photochemistry of soot in the liquid phase but also reveal the significant implications of soot photoaging in the aqueous phase by the release and degradation of organic matter.

Heterogeneous oxidation of SO2 on mineral dust is a significant source of sulfate in the atmosphere. Given that a large fraction of nitrate is deposited on the mineral aerosols, the determination o...

Most solar-energy conversion applications are based on trapping and transferring photoinduced electrons on oxide semiconductor nanoparticles, such as titanium dioxide, and broad UV-vis absorption (400~800 nm) and monotonic IR absorption (1100~3000 cm−1) signals have long been considered signatures of the electron-trapping state on titanium dioxide nanoparticles. Here we show that, under proton-free conditions and using iodide ions in acetonitrile as the hole scavenger, the intrinsic electron-trapping feature of titanium dioxide nanoparticles does not exhibit the characteristic UV-vis absorption and infrared absorption signatures. Further electron spin resonance studies identify the proton-free electron-trapping state as the lattice octahedral Ti6c3+ species, differing from the traditional proton-participating surface tetrahedral Ti4c3+ species. Synchronized radiation ultraviolet photoelectron spectroscopy results also show that the internal electron-trapping state without protons has a larger Ti3d binding energy (1.8 eV) than the blue electron-trapping state (1.3 eV) that forms when protons participate and thus shows different electron transfer abilities. Irradiation of titanium dioxide creates electronically trapped states which play a key role in solar energy conversion. Here, intrinsic electron trapping under aprotic conditions is experimentally shown to exhibit different spectroscopic properties than the conventional blue colour observed under protic conditions.

A large number of fluorinated chemicals have been synthesized and used worldwide because of their unique properties. However, because of the strong C–F bond, fluorinated chemicals are not decomposed in nature. Herein, the activity of gallium oxide toward the degradation of trifluoromethyl benzoic acid in aqueous media was examined under UVC radiation by using a low-pressure mercury lamp as the light source. The degradation process was monitored by HPLC, UV–Vis spectroscopy and TOF-MS techniques, which permitted some intermediates to be identified. The defluorination efficiency was greater under a nitrogen atmosphere than in air, with the para-isomer (4-(trifluoromethyl)benzoic acid) being more prone to degradation (ca. 90%). The degradation mechanism was proposed on the basis of the theoretical calculation on the electron density and the intermediate analysis.

Natural photosynthesis proceeded by sequential water splitting and CO2 reduction reactions is an efficient strategy for CO2 conversion. Here, mimicking photosynthesis to boost CO2-to-CO conversion is achieved by using plasmonic Bi as an electron-proton-transfer mediator. Electroreduction of H2O with a Bi electrode simultaneously produces O2 and hydrogen-stored Bi (Bi-Hx). The obtained Bi-Hx is subsequently used to generate electron-proton pairs under light irradiation to reduce CO2 to CO; meanwhile, Bi-Hx recovers to Bi, completing the catalytic cycle. This two-step strategy avoids O2 separation and enables a CO production efficiency of 283.8 μmol g−1 h−1 without sacrificial reagents and cocatalysts, which is 9 times that on pristine Bi in H2 gas. Theoretical/experimental studies confirm that such excellent activity is attributed to the formed Bi-Hx intermediate that improves charge separation and reduces reaction barriers in CO2 reduction.

In this work, photostable coassemblies from a nonphotostable fluorene oligomer (the energy donor) and a photostable oligomer (the energy acceptor) are fabricated. Long-range exciton migration over a net distance of about 370 energy-donor molecules to energy acceptors is demonstrated in such coassemblies. The fast and long energy migration allows harvesting of the excitation energy of energy donors by embedding a small number of energy acceptors for photostability enhancement. Importantly, embedding a small number of energy acceptors in coassemblies causes a negligible negative influence on the electron donation of energy donors that are desired in practical applications. The advantages of the coassemblies fabricated, that is, high photostability without disrupting the electron donation of energy donors, are well illustrated in fluorescence detection of trace explosives where prolonged working life and improved detection capacity are achieved.

In this study, we report the desirable conversion of H2O2 to OH with aquifer sediment activated by ascorbic acid. Although aquifer sediment contained various iron minerals, such as goethite, hematite, montmorillonite, muscovite, chlorite and phlogopite, it could not efficiently activate H2O2 to produce OH. Interestingly, the presence of ascorbic acid dramatically promoted the OH conversion efficiency of H2O2 by aquifer sediment to remediate organic contaminants in groundwater, which was ascribed to the efficient iron cycle of aquifer sediment induced by ascorbic acid. Among these minerals in sediment, goethite and hematite were more reactive than other minerals to activate H2O2 in the presence of ascorbic acid. Although the initial pH could affect the OH conversion efficiency of H2O2, H2O2 could be decomposed by aquifer sediment at pH 3–11 after the introduction of ascorbic acid. Along with the complete degradation of organic contaminants, the final pH of solution increased to 8.3, which was close to the initial pH (8.9) of groundwater. Moreover, packed column of aquifer sediment could also catalyze the H2O2 conversion to OH for the removal of different organic contaminants with adding ascorbic acid, suggesting a new strategy for in situ chemical oxidation remediation of organic contaminated groundwater.

Photochemical aging represents an important transformation process of aerosol particles in the atmosphere, which greatly influences the physicochemical properties and the environmental impact of aerosols. In this work, we find that Beijing urban PM2.5 aerosol particles release substantial HONO, a significant precursor of •OH radicals, into the gas phase during the photochemical aging process. The generation of HONO exhibits a high correlation with the amount of nitrate in PM2.5. The formation rate of HONO becomes gradually decreased with the irradiation time, but can be restored by introducing the acidic proton, indicative of the essential role of the acidic proton in the HONO production. Other environmental factors such as relative humidity, light intensity, and reaction temperature also possess important influences on HONO production. The normalized photolysis rate constant for HONO (JHNO3→HONO) is in the range of 1.22 × 10–5 s–1 ∼ 4.84 × 10–4 s–1, which is 1–3 orders of magnitude higher than the report...

Hematite (α-Fe2O3) is a promising photoanode material for light-driven water splitting to make solar fuels. Herein, boron incorporated hematite photoanodes are successfully fabricated by a simple impregnation treatment in borate solution before annealing the iron oxyhydroxide (FeOOH) precursor. X-ray diffraction, Raman and X-ray photoelectron spectroscopies revealed regional enrichment of boron and oxygen vacancy near the outmost surface of the photoanode, forming a unique heterostructure. The boron modified photoanodes exhibited significantly improved photoelectrochemical (PEC) water oxidation efficiency, with up to 37 times enhancement in photocurrent density, approaching 1.12 mA cm−2 at 1.23 VRHE under AM 1.5 G illumination. Electrochemical impedance spectroscopy demonstrated a more favorable hole transfer process in the modified photoanode, which can be ascribed to the surface heterostructure induced build-in electric field, as well as the increase in carrier density introduced by oxygen vacancy.

A complex two-dimensional (2D) hierarchical heterostructure was fabricated by a sequential two-dimensional seeded self-assembly, which consisted of laterally grown nanotubes from one perylene monomer and terminally elongated nanocoils from a similar perylene monomer on microribbon seeds from a third perylene. Because the nanotube and nanocoil monomers can form kinetically trapped off-pathway aggregates to prevent self-nucleation and have similar molecular organizations to different facets of the seeds, the nanotube and nanocoil monomers preferentially nucleate and grow on the seed sides and terminal ends, respectively, to form a complex 2D hierarchical heterostructure. The strategy used in this work can be extended to fabricate other complex nanoarchitectures from small molecules.

In this work, we fabricated four diphenylcyclopropenone (DPCP) crystals, which involved various molecular interactions encoded in individual molecular structures 1-4. On the basis of crystalline structural analysis and photoresponsive characterization of the resultant single-crystal microribbons 1-4, we demonstrated that the magnitude of molecular interactions could effectively control the quantum chain reaction and the photoresponsive property of the DPCP crystals. The microribbons 1 and 2 having weak molecular interactions exhibited an efficient chain reaction and large mechanical photoresponses (i.e., photomelting and photodeforming), whereas the microribbons 3 and 4 with strong molecular interactions exhibited no chain reaction and mechanical morphology change. Our work presented a new way to achieve molecular crystals with enhanced mechanical photoresponses.

In aqueous TiO2 photocatalytic hydroxylation of weakly polar aromatics, a series of inverse H/D KIEs of 0.7-0.8 were observed, which is different than the normal H/D kinetic isotope effects (KIEs) usually observed for polar aromatics. This result indicated that the oxidation started by photo-induced hvb+ can be the rate-determining step.

In this study, we construct a surface Fenton system with hydroxylamine (NH2OH), goethite (α-FeOOH), and H2O2 (α-FeOOH–HA/H2O2) to degrade various organic pollutants including dyes (methyl orange, methylene blue, and rhodamine B), pesticides (pentachlorophenol, alachlor, and atrazine), and antibiotics (tetracycline, chloramphenicol, and lincomycin) at pH 5.0. In this surface Fenton system, the presence of NH2OH could greatly promote the H2O2 decomposition on the α-FeOOH surface to produce ·OH without releasing any detectable iron ions during the alachlor degradation, which was different from some previously reported heterogeneous Fenton counterparts. Moreover, the ·OH generation rate constant of this surface Fenton system was 102–104 times those of previous heterogeneous Fenton processes. The interaction between α-FeOOH and NH2OH was investigated with using attenuated total reflectance Fourier transform infrared spectroscopy and density functional theory calculations. The effective degradation of organic p...

The light-driven crawling of a molecular crystal that can form three phases, (α, β, and γ) is presented. Laser irradiation of the molecular crystal can generate phase-dependent transient elastic lattice deformation. The resulting elastic lattice deformation that follows scanning irradiation of a laser can actuate the different phases of molecular crystal to move with different velocity and direction. Because the γ phase has a large Young's modulus (ca. 26 GPa), a force of 0.1 μN can be generated under one laser spot. The generated force is sufficient to actuate the γ-formed molecular crystals in a wide dimensional range to move longitudinally at a velocity of about 60 μm min-1 , which is two orders of magnitude faster than the α and β phases.

TiO2-based dye-sensitization cycle is one of the basic strategies for the development of solar energy applications. Although the power conversion efficiency (PCE) of dye-sensitized devices has been improved through constant attempts, the intrinsically fatal factor that leads to the complete failure of the PCE of TiO2-mediated dye-sensitized devices has not yet been determined. Here, by using isotopically labeled MAS–1H NMR, ATR-FTIR spectroscopy (separate H/D and 48Ti/49Ti experiments), and ESR, we revealed that the accumulative formation of Ti–H species on the TiO2 surface is the intrinsic cause of the PCE failure of TiO2-based dye-sensitization devices. Such a Ti–H species is generated from the reduction of hydrogen ions (mostly released from dye carboxyl groups or organic electrolyte) accompanied by electron injection on the surface of TiO2, which deteriorates the PCE mainly by reducing the electrical conductivity of the TiO2 (by a maximum of ∼80%) and the hydrophilic nature of the TiO2 surface (contac...

It is widely believed that anatase TiO2 {001} and {101} surfaces acts as the oxidative and reductive sites in photocatalytic reactions, respectively, which is attributed to their different intrinsic surface structures. However, we demonstrate that the photocatalytic redox preferences of TiO2 {001} and {101} surfaces are determined by the adsorbate-reconstructed surface structure instead of their intrinsic surface structures, which can be modulated by surface protonation/deprotonation.

HO-adduct radicals have been investigated and confirmed as the common initial intermediates in TiO2 photocatalysis and Fenton degradations of water-insoluble aromatics. However, the evolution of HO-adduct radicals to phenols has not been completely clarified. When 4-d-toluene and p-xylene were degraded by TiO2 photocatalysis and Fenton reactions, respectively, a portion of the 4-deuterium or 4-CH3 group (18-100 %) at the attacked ipso position shifted to the adjacent position of the ring in the formed phenols (NIH shift; NIH is short for the National Institutes of Health, to honor the place where this phenomenon was first discovered). The results, combined with the observation of a key dienyl cationic intermediate by in situ attenuated total reflectance FTIR spectroscopy, indicate that, for the evolution of HO-adduct radicals, a mixed mechanism of both the carbocation intermediate pathway and O2 -capturing pathway occurs in both aqueous TiO2 photocatalysis and aqueous Fenton reactions.

Novel, chiral-selective linear nanotubular heterojunctions were achieved by living supramolecular polymerization of perylenediimide (PDI) derivatives. We demonstrate that the chiral seed can effectively bias achiral PDI molecules to polymerize on its ends in the identical helical sense. More interestingly, the chiral seed can bias the opposite enantiomers to grow expitaxially from its ends even in excess amounts relative to the seed. Furthermore, we demonstrate that the biasing effect of the chiral seed on the opposite enantiomer is not dependent on the length of the chiral seed but is related to the intrinsic length of the elongated nanotube from the opposite enantiomer. The fabrication of chiral-selective nanotubes was achieved by application of the unique biasing effect of the chiral seed in living supramolecular self-assembly.

Manipulating the self-assembly pathway is essentially important in the supramolecular synthesis of organic nano- and microarchitectures. Herein, we design a series of photoisomerizable chiral molecules, and realize precise control over pathway complexity with external light stimuli. The hidden single-handed microcoils, rather than the straight microribbons through spontaneous assembly, are obtained through a kinetically controlled pathway. The competition between molecular interactions in metastable photostationary intermediates gives rise to a variety of molecular packing and thereby the possibility of chirality transfer from molecules to supramolecular assemblies.

Hematite is a promising material for solar water splitting; however, high efficiency remains elusive because of the kinetic limitations of interfacial charge transfer. Here, we demonstrate the pivotal role of proton transfer in water oxidation on hematite photoanodes using photoelectrochemical (PEC) characterization, the H/D kinetic isotope effect (KIE), and electrochemical impedance spectroscopy (EIS). We observed a concerted proton-electron transfer (CPET) characteristic for the rate-determining interfacial hole transfer, where electron transfer (ET) from molecular water to a surface-trapped hole was accompanied by proton transfer (PT) to a solvent water molecule, demonstrating a substantial KIE (∼3.5). The temperature dependency of KIE revealed a highly flexible proton transfer channel along the hydrogen bond at the hematite/electrolyte interface. A mechanistic transition in the rate-determining step from CPET to ET occurred after OH(-) became the dominant hole acceptor. We further modified the proton-electron transfer sequence with appropriate proton acceptors (buffer bases) and achieved a greater than 4-fold increase in the PEC water oxidation efficiency on a hematite photoanode.

In this study, the adsorption process of Cr(VI) on the hematite facets was systematically investigated with synchrotron-based Cr K-edge extended X-ray absorption fine structure (EXAFS) spectroscopy, in situ attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy, density-functional theory calculation, and surface complexation models. Structural model fitting of EXAFS spectroscopy suggested that the interatomic distances of Cr-Fe were, respectively, 3.61 Å for the chromate coordinated hematite nanoplates with exposed {001} facets, 3.60 and 3.30 Å for the chromate coordinated hematite nanorods with exposed {001} and {110} facets, which were characteristic of inner-sphere complexation. In situ ATR-FTIR spectroscopy analysis confirmed the presence of two inner-sphere surface complexes with C3ν and C2ν symmetry, while the C3ν and C2ν species were assigned to monodentate and bidentate inner-sphere surface complexes with average Cr-Fe interatomic distances of 3.60 and 3.30 Å, respectively. On the basis of these experimental and theoretical results, we concluded that HCrO4(-) as dominated Cr(VI) species was adsorbed on {001} and {110} facets in inner-sphere monodentate mononuclear and bidentate binuclear configurations, respectively. Moreover, the Cr(VI) adsorption performance of hematite facets was strongly dependent on the chromate complexes formed on the hematite facets.

Photoelectrochemical (PEC) water oxidation has attracted heightened interest in solar fuel production. It is well accepted that water oxidation on hematite is mediated by surface trapped holes, characterized to be the high valent -Fe═O species. However, the mechanism of the subsequent rate-limiting O-O bond formation step is still a missing piece. Herein we investigate the reaction order of interfacial hole transfer by rate law analysis based on electrochemical impedance spectroscopy (EIS) measurement and probe the reaction intermediates by operando Fourier-transform infrared (FT-IR) spectroscopy. Distinct reaction orders of ∼1 and ∼2 were observed in near-neutral and highly alkaline environments, respectively. The unity rate law in near-neutral pH regions suggests a mechanism of water nucleophilic attack (WNA) to -Fe═O to form the O-O bond. Operando observation of a surface superoxide species that hydrogen bonded to the adjacent hydroxyl group by FT-IR further confirmed this pathway. In highly alkaline regions, coupling of adjacent surface trapped holes (I2M) becomes the dominant mechanism. While both are operable at intermediate pHs, mechanism switch from I2M to WNA induced by local pH decrease was observed at high photocurrent level. Our results highlight the significant impact of surface protonation on O-O bond formation pathways and oxygen evolution kinetics on hematite surfaces.

The hole-driving oxidation of titanium-coordinated water molecules on the surface of TiO2 is both thermodynamically and kinetically unfavorable. By avoiding the direct coordinative adsorption of water molecules to the surface Ti sites, the water can be activated to realize its oxidation. When TiO2 surface is covered by the H-bonding acceptor F, the first-layer water adsorption mode is switched from Ti coordination to a dual H-bonding adsorption on adjacent surface F sites. Detailed in situ IR spectroscopy and isotope-labeling studies reveal that the adsorbed water molecules by dual H-bonding can be oxidized to O2 even in the absence of any electron scavengers. Combined with theoretical calculations, it is proposed that the formation of the dual H-bonding structure can not only enable the hole transfer to the water molecules thermodynamically, but also facilitate kinetically the cleavage of O-H bonds by proton-coupled electron transfer process during water oxidation.

Highly fluorescent and photoconductive nanoribbons assembled from an asymmetric perylene diimide (PDI) were used as a dual-mode sensor for sensitive and selective discrimination of two classes of organic amines in the vapor phase, i.e., alkyl amines and aromatic amines.