Effective photocatalysts and their surface engineering are essential for the efficient conversion of solar energy into chemical energy in photocatalyzed organic transformations. Herein, we report an effective approach for structuring Pd nanoparticles (NPs) on exfoliated 2H-WS nanosheets (WS/PdNPs), resulting in hybrids with extraordinary photocatalytic activity in Suzuki reactions under visible light. Pd NPs of different sizes and densities, which can modulate the photocatalytic activity of the as-prepared WS/PdNPs, were effectively structured on the basal plane of 2H-WS nanosheets via a sonic wave-assisted nucleation method without any reductants at room temperature. As the size of Pd NPs on WS/PdNPs increased, their photocatalytic activity in Suzuki reactions at room temperature increased substantially. In addition, it was found that protic organic solvents play a crucial role in activating WS/PdNPs catalysts in photocatalyzed Suzuki reactions, although these solvents are generally considered much less effective than polar aprotic ones in the conventional Suzuki reactions promoted by heterogeneous Pd catalysts. A mechanistic investigation suggested that photogenerated holes are transferred to protic organic solvents, whereas photogenerated electrons are transferred to Pd NPs. This transfer makes the Pd NPs electron-rich and accelerates the rate-determining step, i.e., the oxidative addition of aryl halides under visible light. WS/PdNPs showed the highest turnover frequency (1244 h) for photocatalyzed Suzuki reactions among previously reported photocatalysts.
Visible-light-driven photocatalysis
has been emerging as an efficient
and sustainable approach for chemical transformation in organic reactions,
in which photostable and cost-effective photosensitizers are required
to trigger and promote it. Monolayer WS2 nanosheets smaller
than 120 nm were prepared by means of a modified liquid exfoliation
method, and they showed strong photoluminescence in the visible range
of the electromagnetic spectrum from 450 to 650 nm. These photoactive
WS2 nanosheets were exploited as photocatalysts in the
oxidative coupling reactions of various amines under visible-light
irradiation. They showed excellent photocatalytic activity and reusability
without the loss of their catalytic activity in the visible-light-driven
oxidative coupling reactions of various amines. In addition, the mechanism
responsible for WS2 nanosheet catalyzed imine production
under visible-light irradiation was fully investigated.
Precise control over doping of photocatalysts is required to modulate their photocatalytic activity in visible light‐driven reactions. Here, a single precursor‐employing bottom‐up approach is developed to produce different heteroatom‐doped graphene quantum dots (GQDs) with unique photocatalytic activities. The solvothermal reaction of a norepinephrine precursor with redox active and condensable moieties effectively produces both nitrogen/sulfur codoped GQDs (NS‐GQDs) and nitrogen‐doped GQDs (N‐GQDs) by simply varying solvents (from dimethyl sulfoxide to water) under microwave irradiation. As‐prepared NS‐GQDs and N‐GQDs show similar lateral sizes (3–4 nm) and heights (1–2 nm), but they include different dopant types and doping constitution and content, which lead to changes in photocatalytic activity in aerobic oxidative coupling reactions of various amines. NS‐GQDs exhibit much higher photocatalytic activity in reactions under visible light than N‐GQDs and oxygen‐doped GQDs (O‐GQDs). The mechanism responsible for the outstanding photocatalytic activity of NS‐GQDs in visible light‐driven oxidative coupling reactions of amines is also fully investigated.
In past decade, electrochemical
energy storage gained undivided
attention with the increase in electrical energy demand for the usage
of new technology such as moveable electronics. Li-ion batteries (LIB)
have been the most successful energy storage system with their long-life
cycle and efficiency, lower energy density, and notable cost effectiveness
with small-scale energy storage. However, with large-scale energy
storage and for long duration, work still needs done to make LIB efficient
on such a scale as well. Recently Li–air batteries have been
suggested as potential energy storage systems that can provide the
solution for large- and long-term electrical energy storage. The Li–air
battery utilizes the catalyst-based redox reaction, and still, it
is not applicable commercially due to low current density, poor life
cycle, and energy efficiency. Generally, such problems are associated
with the materials used as an electrocatalyst and on the selection
of the electrolyte. Herein, we briefly review the current advancements
in the field of electrocatalysts for Li–air batteries which
hinders their improvement toward commercial applications, and this
review also provides an outlook for future Li–air battery systems.
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