Earth-abundant
nickel is a typical non-noble-metal cocatalyst used
for photocatalytic hydrogen evolution (PHE). Ni nanoparticles, however,
tend to aggregate during the hydrogen production process, significantly
lowering their PHE activity. To avoid aggregation, we used single
atom form Ni and anchored them on vacancies in nitrogen-doped graphene
(Ni-NG) as a cocatalyst for PHE. We demonstrated that Ni-NG is a robust
and highly active cocatalyst for PHE from water. With only 0.0013
wt % of Ni loading, the PHE activity of composite Ni-NG/CdS photocatalyst
improves by 3.4 times compared to that of NG/CdS, and it does not
decay even after 10 rounds of 5-hour running. The quantum efficiency
of Ni-NG/CdS for PHE reaches 48.2% at 420 nm, one of the highest efficiencies
for non-noble-metal-based cocatalysts reported in the literature.
Photoluminescence spectral analyses and electrochemical examinations
indicated that Ni-NG coupled to CdS serves not only as an electron
storage medium to suppress electron–hole recombination but
also as an active catalyst for proton reduction reaction. Density
functional theory calculations show that the high activity of Ni-NG/CdS
composite results from the single Ni atoms trapped in NG vacancies,
which significantly reduces the activation energy barrier of the hydrogen
evolution reaction. This research may be valuable for developing robust
and highly active noble metal free cocatalysts for solar hydrogen
production.
Organic luminogens constitute promising prototypes for various optoelectronic applications. Since gaining distinct color emissions normally requires the alternation of the conjugated backbone, big issues remain in material synthetic cost and skeleton compatibility while pursuing full‐color luminescence. Upon a facile one‐step coupling, three simple but smart perchalcogenated (O, S, and Se) arenes are synthesized. They exhibit strong luminescent tricolor primaries (i.e., blue, green, and red, respectively) in the solid state with a superior quantum yield up to >40% (5–10 times higher than that in corresponding solutions). The properties originate from a fluorescence–phosphorescence–phosphorescence triple‐channel emission effect, which is regulated by S and Se heavy atoms–dependent intersystem crossing upon molecular packing, as well as Se–Se atom interaction–caused energy splittings. Consequently, full‐color luminescence, including a typical white‐light luminescence with a Commission Internationale de I'Eclairage coordinate of (0.30, 0.35), is realized by complementarily incorporating these tricolor luminescent materials in the film. Moreover, mechanochromic luminescent color conversions are also observed to achieve the fine‐tuning of the luminescent tints. This strategy can be smart to address full‐color luminescence on the same molecular skeleton, showing better material compatibility as an alternative to the traditional multiple‐luminophore engineering.
In this paper, we demonstrate for the first time the use of gliadin particles to structure algal oil (rich in DHA) and to exert chemical stability against lipid oxidation via the Pickering high internal phase emulsion (HIPE) strategy. The gliadin/chitosan colloid particles (GCCPs) were effectively adsorbed and anchored at the algal oil-water interface. Concomitantly, the particle-coated droplets as building blocks constructed a percolating 3D-network framework, endowing Pickering HIPEs with viscoelastic and self-supporting attributes. In addition, Pickering HIPEs loaded with shell (HIP-curEs) or core curcumin (HIPEs-cur) were constructed to depress the oxidation of algal oil. The content of primary (lipid hydroperoxides) and secondary (malondialdehyde and hexanal) oxidation products in HIPEs was lower than that in bulk oil. The oxidative stability of HIPEs was further improved in shell and core curcumin. An in vitro gastrointestinal (GI) model was constructed to characterize the lipid digestion, lipid oxidation as well as curcumin bioaccessibility of the ingested Pickering HIPEs. Lipid oxidation in the Pickering HIPEs was retarded under GI fluids, especially in the presence of core curcumin. The free fatty acid (FFA) fraction released was below 30% for all HIPEs, reflecting that the Pickering HIPEs formed restrict the digestion of fat or oil and potentially help to fight obesity. Interestingly, this route enhanced the bioaccessibility of curcumin from only 2.13% (bulk algal oil) to 53.61% (core curcumin); in particular, it reached 76.82% for shell curcumin. These results help to fill the gap between the physicochemical performance of the gliadin particle stabilized Pickering HIPEs and their potential applications as oral delivery systems of nutraceuticals. This work opens concomitantly an attractive strategy to convert liquid oils into antioxidant soft solids without artificial trans fats, as a potential alternative for PHOs.
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