Bromo-terminated polystyrene (PSt-Br) and poly(methyl methacrylate) (PMMA-Br) with designed molecular weights and narrow molecular weight distributions were prepared by atom transfer radical polymerization (ATRP). These bromo-terminated polymers were allowed to react with C60 under ATRP conditions to yield C60-end-bonded PSt (PSt-C60-Br) and PMMA (PMMA-C60-Br). The polymers were characterized by gel permeation chromatography (GPC), UV-vis, FT-IR, and fluorescence spectra. GPC profiles obtained by UV and RI dual detectors indicated that C60 had been covalently bonded to the polymers, and most of the C60-end-bonded polymers were monosubstituents. Furthermore, 2-aminoacetonitrile (AAN) was used as an IR label to react with PSt-C60-B; the products thus obtained show a characteristic absorption of CN group at 2369 cm -1 . This result reinforces the conclusion that C60 has been covalently bonded into the polymer. The fluorescence of PMMA-C60-Br and PSt-C60-Br can be quenched by triethylamine or fumaronitrile, indicating that C60 still keeps its strong electron-accepting and strong electron-donating property after it was modified by macromolecules. A possible mechanism of the formation of C60-end-bonded PSt was deduced tentatively.

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Designing a semiconductor‐based heterostructure photocatalyst for achieving the efficient separation of photogenerated electron‐hole pairs is highly important for enhancing H2 releasing photocatalysis. Here, a new class of Ni1−xCoxSe2–C/ZnIn2S4 hierarchical nanocages with abundant and compact ZnIn2S4 nanosheets/Ni1−xCoxSe2C nanosheets 2D/2D hetero–interfaces, is designed and synthesized. The constructed heterostructure photocatalyst exposes rich hetero‐junctions, supplying the broad and short transfer paths for charge carriers. The close contacts of these two kinds of nanosheets induce a strong interaction between ZnIn2S4 and Ni1−xCoxSe2C, improving the separation and transfer of photo‐generated electron‐hole pairs. As a consequence, the distinctive Ni1−xCoxSe2C/ZnIn2S4 hierarchical nanocages without using additional noble‐metal cocatalysts, display remarkable H2‐relaesing photocatalytic activity with a rate of 5.10 mmol g−1 h−1 under visible light irradiation, which is 6.2 and 30 times higher than those of fresh ZnIn2S4 nanosheets and bare Ni1−xCoxSe2C nanocages, respectively. Spectroscopic characterizations and theory calculations reveal that the strong interaction between ZnIn2S4 and Ni1−xCoxSe2C 2D/2D hetero‐interfaces can powerfully promote the separation of photo‐generated charge carriers and the electrons transfer from ZnIn2S4 to Ni1−xCoxSe2C.

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