A novel CdS/ZnO heterojunction constructed of zero-dimensional (0D) CdS quantum dots (QDs) and two-dimensional (2D) ZnO nanosheets (NSs) was rationally designed for the first time. The 2D ZnO NSs were assembled into ZnO microflowers (MFs) via an ultrasonic-assisted hydrothermal procedure (100 °C, 12 h) in the presence of a NaOH solution (0.06 M), and CdS QDs were deposited on both sides of every ZnO NS in situ by using the successive ionic-layer absorption and reaction method. It was found that the ultrasonic treatment played an important role in the generation of ZnO NSs, while NaOH was responsible to the assembly of a flower-like structure. The obtained CdS/ZnO 0D/2D heterostructures exhibited remarkably enhanced photocatalytic activity for hydrogen evolution from water splitting in comparison with other CdS/ZnO heterostructures with different dimensional combinations such as 2D/2D, 0D/three-dimensional (3D), and 3D/0D. Among them, CdS/ZnO-12 (12 deposition cycles of CdS QDs) exhibited the highest hydrogen evolution rate of 22.12 mmol/g/h, which was 13 and 138 times higher than those of single CdS (1.68 mmol/g/h) and ZnO (0.16 mmol/g/h), respectively. The enhanced photocatalytic activity can be attributed to several positive factors, such as the formation of a Z-scheme photocatalytic system, the tiny size effect of 0D CdS QDs and 2D ZnO NSs, and the intimate contact between CdS QDs and ZnO NSs. The formation of a Z-scheme photocatalytic system remarkably promoted the separation and migration of photogenerated electron-hole pairs. The tiny size effect effectively decreased the recombination probability of electrons and holes. The intimate contact between the two semiconductors efficiently reduced the migration resistance of photogenerated carriers. Furthermore, CdS/ZnO-12 also presented excellent stability for photocatalytic hydrogen evolution without any decay within five cycles in 25 h.

Rational design of CdS@ZnO core-shell structure via atomic layer deposition for drastically enhanced photocatalytic H evolution with excellent photostability, Nano Energy, http://dx.doi.org/10. 1016/j.nanoen.2017.06.047 This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting galley proof before it is published in its final citable form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain. number of deposition cycles, and the obtained CdS@ZnO with 100 ALD deposition cycles displays the optimal photocatalytic H 2 evolution rate of 11.36 mmol/g/h. WhenPt and PdS are used as the co-catalysts, the H 2 evolution rates are further enhanced to 71.39 and 98.82 mmol/g/h, respectively, which are 4.1 and 5.7 times higher than the highest reported value (17.40 mmol/g/h) among CdS-ZnO catalyst systems. Detailed characterization reveals that the drastically enhanced photocatalytic activity can be attributed to not only efficient space separation of the photo-induced electrons and holes resulted from the formation of a direct Z-scheme photocatalytic system between crystalline ZnO and CdS, but also the intimate contact at molecular scale between the two semiconductors. Due to the coverage of ALD-prepared crystalline ZnO shell on CdS core, the CdS@ZnO core-shell structures exhibit excellent photostability. Graphical abstract3 / 31

Two-dimensional/two-dimensional (2D/2D) stacking heterostructures are highly desirable in fabricating efficient photocatalysts because face-to-face contact can provide a maximized interfacial region between the two semiconductors; this largely facilitates the migration of charge carriers. Herein, a WS /graphitic carbon nitride (CN) 2D/2D nanosheet heterostructure decorated with CdS quantum dots (QDs) has been designed, for the first time. Optimized CdS/WS /CN without another cocatalyst exhibits a significantly enhanced photocatalytic H evolution rate of 1174.5 μmol h g under visible-light irradiation (λ>420 nm), which is nearly 67 times higher than that of the pure CN nanosheets. The improved photocatalytic activity can be primarily attributed to the highly efficient charge-transfer pathways built among the three components, which effectively accelerate the separation and transfer of photogenerated electrons and holes, and thus, inhibit their recombination. Moreover, the extended light-absorption range also contributes to excellent photocatalytic efficiency. In addition, the CdS/WS /CN photocatalyst shows excellent stability and reusability without apparent decay in the photocatalytic H evolution within 4 cycles in 20 h. It is believed that this work may shed light on specifically designed 2D/2D nanosheet heterostructures for more efficient visible-light-driven photocatalysts.

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One-pot three-component regioselective azidealkyne cycloadditions are central reactions for synthesizing pharmaceuticals and fine chemicals and are also applied for in vivo metabolic labeling biotechnology. Homogeneous catalysts based on copper species coordinated with ancillary ligands are regularly used to perform this reaction, offering superior catalytic activity and selectivity compared to conventional heterogeneous counterparts based on supported copper nanoparticles. However, the challenge of catalyst recovery limits the use of these homogeneous compounds in many large-scale applications. In this work, we report the high catalytic performance of a family of Cu-based single-atom catalysts for triazole synthesis, with an emphasis on the fundamental understanding of the structure and function of the catalyst. The catalysts were prepared via tricyanomethanide polymerization to create a joint electronic structure where the mesoporous graphitic carbon nitride carrier acts as a ligand for the atomically dispersed copper species. The material properties and the precise metal location/coordination (i.e., deposited in the heptazine pore of carbon nitride, substituted in the framework of carbon nitride, hosted in a vacancy, or entrapped in sandwich-like arrangement) were characterized through a battery of spectroscopic and theoretical methods. The catalysts were employed in the synthesis of 1,2,3-triazoles employing azide-alkyne click reaction under base-free conditions. The single-atom Cu catalysts demonstrated improved activity and selectivity compared to the homogeneous reference catalyst. Density functional theory calculations corroborated the results and showed that the reaction proceeds through a barrier given by the activation of the acetylenic moiety on Cu 1 . The activity of this step was primarily affected by the coordination of the metal with the support. Therefore, understanding the metal coordination in single-atom catalysts is critical to further optimizing single-atom catalysts and greening synthetic chemistry.