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3 N 4 /SnS yolk−shell Z-scheme photocatalysts are fabricated by a simple template-assisted strategy. The L-cysteine can offer the amine groups and meanwhile anchor on the surface of g-C 3 N 4 during solvothermal reaction and thus contributes greatly to the enhanced carbon dioxide adsorption capability. This Zscheme photocatalytic reduction mechanism of Au@g-C 3 N 4 /SnS performs valuable functions in the reaction, leading to CH 4 generation much earlier and higher concentration than that of Au@g-C 3 N 4 . Meanwhile, the unique yolk−shell structure can make the light bounce back and forth in the cavity and thus enhances the availability ratio of light. The application of small amount of noble metal cocatalysts and the large Brunauer−Emmett−Teller surface areas are also benefited for the enhanced photocatalytic activities. Hence, this novel material exhibits a distinguished reduction performance for CO 2 reduction under visible light. The highest yields of CH 4 (3.8 μmol g −1 ), CH 3 OH (5.3 μmol g −1 ), and CO (17.1 μmol g −1 ) can be obtained for the sample of Au@g-C 3 N 4 /SnS (SnS 41.5%), which is higher than other latest reported g-C 3 N 4based photocatalysts for CO 2 photoreduction including coupled with semiconductors and noble metal cocatalysts. This strategy might represent a novel way for the effective transition of CO 2 to clean fuels and can also be enormous feasible utilization in the photocatalytic field.

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The free radical polymerization of acrylates photo-initiated by push-pull dye-based photoinitiating systems (PISs) is widely investigated in previous works. As a supplementary investigation on push-pull dyes, here in this article, 25 push-pull structures comprising electron acceptors derived from indane-1,3-dione and 1H-cyclopenta[b]naphthalene-1,3(2H)-dione (series 1) and 4-dimethoxyphenyl-1-allylidene moieties (series 2) and various electron donors are synthesized and examined as innovative structures for photoinitiation. Among the two series of dyes examined in this work and by monitoring the polymerization processes by RT-FTIR measurements, four dyes are determined as exhibiting excellent photoinitiation performances and these dyes are selected to perform further studies concerning the chemical mechanisms occurring inside the three-component PISs, for example, steady state photolysis, fluorescence quenching measurements, and cyclic voltammetry. Markedly, their reactivity is also proved by photoinitiation performance upon sunlight. These results prompt us to develop high performance push-pull dyes as photosensitizers and sunlight can be used as a mild and ecofriendly light source, which can advantageously replace LEDs for the free radical photopolymerization in the future. Finally, the formation of 3D patterns with an excellent gradient of resolution is successfully achieved by the direct laser write (DLW) with/without silica fillers.