Solar‐Driven Production Of Hydrogen Peroxide And Benzaldehyde In Two‐Phase System By An Interface‐Engineered Co₉S₈‐CoZnIn₂S₄ Heterostructure

Abstract

Coupling the photoproduction of solar fuel and value‐added chemicals is highly attractive, as it maximizes the utilization of incident sunlight and the economic value of photocatalytic reactions. Constructing intimate semiconductor heterojunction for these reactions is highly desirable due to accelerated charge separation at the interfacial contact, but is challenged by material synthesis. Here, an active heterostructure bearing intimate interface, consisting of discrete Co9S8 nanoparticles anchored on cobalt doped ZnIn2S4 using a facile in situ one‐step strategy, can drive photocatalytic co‐production of H2O2 and benzaldehyde from a two‐phase water/benzyl alcohol system with spatial product separation is reported. The heterostructure yields a high production amount of 49.5 and 55.8 mmol L−1 for H2O2 and benzaldehyde under visible‐light soaking, respectively. The synchronous elemental Co doping and intimate heterostructure establishment substantially improve the overall reaction kinetics. Mechanism studies reveal that H2O2 generated in the aqueous phase undergoes photodecomposition forming hydroxyl radical, which is subsequently transferred into the organic phase to oxidize benzyl alcohol into benzaldehyde. This study offers fertile guidelines for creating integrated semiconductors and broadens the avenue toward the coupled production of solar fuels and industrially important chemicals.

Engineering of Pore Design and Oxygen Vacancy on High-Entropy Oxides by a Microenvironment Tailoring Strategy

“…17 Notably, the benzyl alcohol oxidation strategy receives widespread consideration for the feasible availability of the raw material for benzyl alcohol, the simplicity of the preparation process, and the environmental friendliness of the manufacturing procedure. 3 Furthermore, molecular oxygen offers the advantages of economic and environmental protection, abundant reserves, and high atomic utilization as oxidants. 18 However, the highly efficiency activation of molecular oxygen is hindered by harsh conditions (e.g., high temperature and pressure).…”

“…Benzaldehyde, a high-value-added product, is extensively applied in pharmaceuticals, fine chemicals, spices, dyestuffs, pesticides, etc . Notably, the benzyl alcohol oxidation strategy receives widespread consideration for the feasible availability of the raw material for benzyl alcohol, the simplicity of the preparation process, and the environmental friendliness of the manufacturing procedure . Furthermore, molecular oxygen offers the advantages of economic and environmental protection, abundant reserves, and high atomic utilization as oxidants .…”

“…1,2 The structural variety of cationic and anionic sites grants HEOs with various crystal phases (e.g., perovskite, fluorite, rock-salt, and spinel). 3 The maximized conformational entropy facilitates the enhancement of intermetallic solubility, suppression of phase segregation, and maintenance of structural stability even under harsh conditions. 4 Hence, it is a new material utilized in various applications (energy storage and conversion, sensors, photoelectric devices, and catalysts).…”

“…High-entropy oxides (HEOs), the formation of five or considerably more elements in near equimolar, attract growing consideration for their versatile redox property and rich cation constitutions, as well as brilliant thermal and chemical stability among the plurality of complicated metal oxides. , The structural variety of cationic and anionic sites grants HEOs with various crystal phases (e.g., perovskite, fluorite, rock-salt, and spinel) . The maximized conformational entropy facilitates the enhancement of intermetallic solubility, suppression of phase segregation, and maintenance of structural stability even under harsh conditions .…”

1D Covalent Organic Frameworks Triggering Highly Efficient Photosynthesis of H2O2 via Controllable Modular Design

“…Hence, this can be considered a typical 2-electron oxygen reduction reaction path in the H 2 O 2 photosynthesis of this system. [26] Moreover, the control experiments were conducted using additional substances to trap active species within the photocatalytic redox process, for instance, benzoquinone (BQ) as the superoxide radical ( * O 2 À ), ethylene diamine tetraacetic acid disodium salt (EDTA-2Na) as the hole (h + ), t-butyl alcohol (TBA) as the hydroxyl radical ( * OH), AgNO 3 as the electron (e À ) scavengers. As shown in Figure 4c, in the presence of AgNO 3 or BQ, the photocatalytic reaction has been severely hampered, indicating the indispensable role of O 2 and active electrons.…”