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High‐efficient photoelectrocatalytic direct ammonia oxidation reaction (AOR) conducted on semiconductor photoanodes remains a substantial challenge. Herein, we develop a strategy of simply introducing ppm levels of Cu ions (0.5–10 mg/L) into NH3 solutions to significantly improve the AOR photocurrent of bare BiVO4 photoanodes from 3.4 to 6.3 mA cm−2 at 1.23 VRHE, being close to the theoretical maximum photocurrent of BiVO4 (7.5 mA cm−2). The surface charge‐separation efficiency has reached 90 % under a low bias of 0.8 VRHE. This AOR exhibits a high Faradaic efficiency (FE) of 93.8 % with the water oxidation reaction (WOR) being greatly suppressed. N2 is the main AOR product with FEs of 71.1 % in aqueous solutions and FEs of 100 % in non‐aqueous solutions. Through mechanistic studies, we find that the formation of Cu−NH3 complexes possesses preferential adsorption on BiVO4 surfaces and efficiently competes with WOR. Meanwhile, the cooperation of BiVO4 surface effect and Cu‐induced coordination effect activates N−H bonds and accelerates the first rate‐limiting proton‐coupled electron transfer for AOR. This simple strategy is further extended to other photoanodes and electrocatalysts. [ABSTRACT FROM AUTHOR]

The sluggish H2O oxidation kinetics on photoanodes severely obstructs the overall solar‐to‐energy efficiency of photoelectrochemical (PEC) cells. Herein, we find a 10 to 55‐fold increase of photocurrent by conducting ammonia oxidation reaction (AOR) on hematite (α‐Fe2O3) photoanodes under near‐neutral pH (9–11) and moderate applied potentials (1.0–1.4 VRHE) compared to H2O oxidation. By rate law analysis and operando spectroscopic studies, we confirm the non‐radical nucleophilic attack of NH3 molecules on high‐valent surface Fe−O species (e.g. FeIV=O) and Fe−N species that produces NOx− and N2, respectively, which overwhelms the nucleophilic attack of H2O on surface FeIV=O and contributes to a high Faradaic efficiency of above 80 % for AOR. This work reveals a novel non‐radical nucleophilic attack strategy, which is significantly different from the conventional indirect radical‐mediated AOR mechanism, for the rational design of high‐performance AOR photoelectrocatalysts. [ABSTRACT FROM AUTHOR]

Abstract: Visible light has risen to become a very important facilitator for selective radical reactions enabled by well‐cognized photocatalysts. The renaissance of visible‐light photocatalysis on this matter partly relies on integrating it with other fields of catalysis. In parallel, 2,2,6,6‐tetramethylpiperidin N‐oxide (TEMPO), a quintessential persistent radical, has a wide range of uses owing to its exceptional redox behavior, which gives rise to its latest prominence in catalysis. Therefore, integrating the catalysis of TEMPO with photocatalysis to perform visible‐light‐induced selective reactions becomes a very convenient marriage of merits. In this context, the integration of different types of photocatalysts, including metal complexes, metal‐free organic dyes, and semiconductors, with TEMPO for outstanding organic transformations will be summarized. To expand further the catalytic repertoire, the integration of TEMPOH analogues such as NHPI (N‐hydroxyphthalimide) and NHS (N‐hydroxysuccinimide) with photocatalysis will also be discussed. Hopefully, these advances will pave the way for more breakthroughs by integrating TEMPO and its analogues with photocatalysis to lead to a valuable blueprint for visible‐light‐induced selective organic transformations. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

The title reaction provides sulfoxides together with small amounts of the corresponding sulfones. [ABSTRACT FROM AUTHOR]

The relationship between oxygen vacancy (OV) concentration of semiconductors and their photocatalytic performances is far from clarified. In this study, by tuning the OV concentration of BiOCl (001) surface via a novel H 2 O 2 treatment coupled infrared irradiation method, we demonstrate that OV concentration of BiOCl (001) surface strongly determine its surface atomic and electronic structures to modulate the photocatalytic pathways. Being of shorter Bi Bi and Bi O bond lengths as well as more electrons being less localized, BiOCl (001) surface with higher OV concentration favored molecular oxygen activation to generate O 2 2− via a two-electron transfer pathway, while the generated O 2 2− could prevent the over oxidation of amines and thus achieve high selectivity in the oxidation of amines to imines. Similar phenomena were also observed for other semiconductor photocatalysts such as TiO 2 and Nb 2 O 5 , suggesting the generality of oxygen vacancy concentration mediated selectivity enhancement. These findings shed light on the relationship between the oxygen vacancy concentration and the surface structure of semiconductor photocatalysts and offer a novel pathway to realize photocatalytic selective oxidation of amines to imines. [ABSTRACT FROM AUTHOR]

TiO2 acts as a photocatalyst in the synergistic aerobic oxidation of aryl sulfides and benzylamines. [ABSTRACT FROM AUTHOR]