An oxygenation pathway: The title transformation involves a two-step process: selective step to generate aldehyde intermediates and subsequent condensation afford the imine products (see scheme). Detailed facts of importance specialist readers are published as "Supporting Information". Such documents peer-reviewed, but not copy-edited or typeset. They made available submitted by authors. Please note: publisher is responsible for content functionality any supporting information supplied Any...

Nonmetal P-doped hematite photoanodes with remarkably improved photocurrent densities were synthesized. The high activity is attributed to the enhanced electron mobility.

Semiconductor-based photocatalysis is an ideal method for air purification by eliminating nitrogen oxide (NO). However, sluggish carrier separation, photocatalysts deactivation and incomplete oxidation are significant bottlenecks photocatalytic treatment of indoor pollutant NO. Herein, ZnO with assorted structures fabricated undergoes further modification deliberate surface defect constructions. Utilized flux agents during the synthesis provide a more feasible reducing atmosphere, under...

Phosphate modified TiO2 photocatalysts were prepared by phosphoric acid treatment before or after crystallization. Substrates with different structures chosen to explore the photocatalytic activity of as-modified under UV irradiation. It was found that effect phosphate modification is definitely attributed surface-bound anion, and can affect both rates pathways reactions, which are great dependence on properties substrates. The degradation substrates (such as 4-chloropehenol, phenol,...

Well-defined ultrathin nanoribbons have been fabricated from an amphiphilic electron donor-acceptor (D-A) supramolecule comprising perylene tetracarboxylic diimide as the backbone scaffold to enforce one-dimensional intermolecular assembly via strong pi-stacking. These demonstrated high photoconductivity upon illumination with white light. The thus obtained is likely due optimal molecular design that enables a good kinetic balance between two competitive processes, intramolecular charge...

A representative polyoxometalate, alpha-12-tungstophosphatic acid (PW12(3-), POM), is loaded on the surface of TiO2 particles used as a cocatalyst to gain further insights into underlying reaction mechanism and estimate feasibility using new POM/TiO2 in photocatalytic degradation 2,4-dichlorophenol (DCP) aqueous media. Loading PW12(3-) species enhances charge separation UV-illuminated TiO2, thereby accelerating hydroxylation initial DCP substrate but not mineralization DCP, which somewhat...

Photoelectrocatalytic degradation of various dyes under visible light irradiation with a TiO2 nanoparticles electrode has been investigated to reveal the mechanism for TiO2-assisted photocatalytic dyes. The both cationic and anionic at different biases, including change in rate photocurrent bias potential, degraded intermediates, voltage-induced adsorption dyes, accumulation electrons electrode, effect additives such as benzoquinone (BQ) N,N-dimethyl aniline (DMA), formation active oxygen...

Imines are important intermediates for the synthesis of fine chemicals, pharmaceuticals, and agricultural chemicals. Selective oxidation amines into their corresponding imines with dioxygen is one most-fundamental chemical transformations. Herein, we report a series benzylic atmospheric as oxidant on surface anatase TiO(2) under visible-light irradiation (λ>420 nm). The response this system was caused by formation complex through adsorption amine onto TiO(2). From analysis products specially...

The hole-driving oxidation of titanium-coordinated water molecules on the surface TiO2 is both thermodynamically and kinetically unfavorable. By avoiding direct coordinative adsorption to Ti sites, can be activated realize its oxidation. When covered by H-bonding acceptor F, first-layer mode switched from coordination a dual adjacent F sites. Detailed in situ IR spectroscopy isotope-labeling studies reveal that adsorbed oxidized O2 even absence any electron scavengers. Combined with...

Hematite is a promising material for solar water splitting; however, high efficiency remains elusive because of the kinetic limitations interfacial charge transfer. Here, we demonstrate pivotal role proton transfer in oxidation on hematite photoanodes using photoelectrochemical (PEC) characterization, H/D isotope effect (KIE), and electrochemical impedance spectroscopy (EIS). We observed concerted proton-electron (CPET) characteristic rate-determining hole transfer, where electron (ET) from...

Relay race: By using polyprotic-acid-based pendant proton relays (phosphate, L-glutamic acid, and malonic acid), the oxygen reduction reaction (ORR) on a TiO2 surface is switched from single-electron process to concerted 4 e−/4 H+ H2O. In contrast, monocarboxylic acids (PA AA) without only enhance ORR rate but barely change pathway. As service our authors readers, this journal provides supporting information supplied by authors. Such materials are peer reviewed may be re-organized for online...

Light-driven dual catalysis that combines photosensitizers and transition-metal complexes has become a powerful approach for diverse cross-coupling reactions. Heterogeneous photocatalysts recently have gained growing attention to build such catalytic system controllable reaction kinetics enhanced activity. Incorporating metal catalyst into the framework of photocatalyst could endow unique metallaphotoredox platforms. Herein, we assemble carbon nitride nickel (C3N4–Ni) via direct coordination...

Prospects in light-driven water activation have prompted rapid progress hydrogenation reactions. We describe a Ni2+ -N4 site built on carbon nitride for catalyzed semihydrogenation of alkynes, with supplying protons, powered by visible-light irradiation. Importantly, the photocatalytic approach developed here enabled access to diverse deuterated alkenes D2 O excellent deuterium incorporation. Under irradiation, evolution four-coordinate species into three-coordinate Ni+ was spectroscopically...

The water oxidation half-reaction at anodes is always considered the rate-limiting step of overall splitting (OWS), but actual bias distribution between photoanodes and cathodes photoelectrochemical (PEC) OWS cells has not been investigated systematically. In this work, we find that, for PEC consisting (nickel-modified

Selective oxidation of benzylic amines to imines with atmospheric O2 is achieved in water on TiO2 under UV irradiation. The afforded imine could be easily separated and can recycled by filtration. To scale up, gram-scale products obtained.

The reaction pathways by which oxygen is incorporated into the substrate in photocatalytic oxidation of terephthalic acid (TPTA) are vastly different on {001} and {101} facets an anatase single crystal. This was established controlling percentage facets, isotopically tracing origins hydroxy group, studying dioxygen consumption variance concentration hydroxylation intermediate. Detailed facts importance to specialist readers published as "Supporting Information". Such documents peer-reviewed,...

Accelerating proton transfer has been demonstrated as key to boosting water oxidation on semiconductor photoanodes. Herein, we study proton-coupled electron (PCET) of five typical photoanodes [i.e., α-Fe2O3, BiVO4, TiO2, plasmonic Au/TiO2, and nickel-iron oxyhydroxide (Ni1-xFexOOH)-modified silicon (Si)] by combining the rate law analysis H2O molecules with H/D kinetic isotope effect (KIE) operando spectroscopic studies. An unexpected universal half-order kinetics is observed for H2O,...

N→O→N: Die Titelumsetzung verläuft als zweistufiger Prozess: In einem selektiven Oxygenierungsschritt werden Aldehydintermediate gebildet, und diese in anschließenden Kondensationsschritt zu den Iminprodukten umgesetzt (siehe Schema). Detailed facts of importance to specialist readers are published as "Supporting Information". Such documents peer-reviewed, but not copy-edited or typeset. They made available submitted by the authors. Please note: The publisher is responsible for content...

Let′s facet it: TiO2 mesocrystals (MCs; see figure) enclosed by (101) and (001) facets can be synthesized a facile green approach the ratio of (101)/(001) tuned simply adjusting solvothermal periods. The photocatalytic activity MCs exposing high proportions possess higher than those with lower facets; this attributed to synergistic effect Ti3+ ratio. Detailed facts importance specialist readers are published as "Supporting Information". Such documents peer-reviewed, but not copy-edited or...

TiO2-based dye-sensitization cycle is one of the basic strategies for development solar energy applications. Although power conversion efficiency (PCE) dye-sensitized devices has been improved through constant attempts, intrinsically fatal factor that leads to complete failure PCE TiO2-mediated not yet determined. Here, by using isotopically labeled MAS-1H NMR, ATR-FTIR spectroscopy (separate H/D and 48Ti/49Ti experiments), ESR, we revealed accumulative formation Ti-H species on TiO2 surface...

To gain an atomic-level understanding of the relationship among surface structure, interfacial interaction, and water oxidation activity on TiO2, we studied adsorption its photocatalytic anatase TiO2 with {101} {001} exposed surfaces by in situ infrared spectroscopy, kinetic isotope effect studies, density functional theory (DFT)-based molecular dynamics calculations. Our experimental results demonstrate that reaction occurs exclusively hydrogen-bonded molecules (via hydroxyls) over surface,...