It is curial to develop a high-efficient, low-cost visible-light responsive photocatalyst for the application in solar energy conversion and environment remediation. Here, a three-dimensional (3D) porous g-C3N4/graphene oxide aerogel (CNGA) has been prepared by the hydrothermal coassembly of two-dimensional g-C3N4 and graphene oxide (GO) nanosheets, in which g-C3N4 acts as an efficient photocatalyst, and GO supports the 3D framework and promotes the electron transfer simultaneously. In CNGA, the highly interconnected porous network renders numerous pathways for rapid mass transport, strong adsorption and multireflection of incident light; meanwhile, the large planar interface between g-C3N4 and GO nanosheets increases the active site and electron transfer rate. Consequently, the methyl orange removal ratio over the CNGA photocatalyst reaches up to 92% within 4 h, which is much higher than that of pure g-C3N4 (12%), 2D hybrid counterpart (30%) and most of representative g-C3N4-based photocatalysts. In addition, the dye is mostly decomposed into CO2 under natural sunlight irradiation, and the catalyst can also be easily recycled from solution. Significantly, when utilized for CO2 photoreduction, the optimized CNGA sample could reduce CO2 into CO with a high yield of 23 mmol g(-1) (within 6 h), exhibiting about 2.3-fold increment compared to pure g-C3N4. The photocatalyst exploited in this study may become an attractive material in many environmental and energy related applications.

A tubular g-C3 N4 isotype heterojunction (TCNH) photocatalyst was designed for cooperative manipulation of the oriented transfer of photogenerated electrons and holes to pursue high catalytic performance. The adduct of cyanuric acid and melamine (CA·M) is first hydrothermally treated to assemble into hexagonal prism crystals; then the hybrid precursors of urea and CA·M crystals are calcined to form tubular g-C3 N4 isotype heterojunctions. Upon visible-light irradiation, the photogenerated electrons transfer from g-C3 N4 (CA·M) to g-C3 N4 (urea) driven by the conduction band offset of 0.05 eV, while the photogenerated holes transfer from g-C3 N4 (urea) to g-C3 N4 (CA·M) driven by the valence band offset of 0.18 eV, which renders oriented transfer of the charge carriers across the heterojunction interface. Meanwhile, the tubular structure of TCNH is favorable for oriented electron transfer along the longitudinal dimension, which greatly decreases the chance of charge carrier recombination. Consequently, TCNH exhibits a high hydrogen evolution rate of 63 μmol h(-1) (0.04 g, λ > 420 nm), which is nearly five times of the pristine g-C3 N4 and higher than most of the existing g-C3 N4 photocatalysts. This study demonstrates that isotype heterojunction structure and tubular structure can jointly manipulate the oriented transfer of electrons and holes, thus facilitating the visible-light photocatalysis.

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Inspired by the bioadhesion mechanism found in mussel, a catechol derivative, 3-(3,4-dihydroxyphenyl)propionic acid (diHPP), is employed as both linker and reducer of Ag + to synthesize the Ag/TiO 2 nanotube (Ag/TNT) heterojunction under ambient conditions in this study. In the prepared Ag/TNT composite, Ag nanocrystals about 3.8 nm in diameter distribute over the TNT surface uniformly and form the heterojunction structure with TNT. The diHPP first links to the TNT surface through the bidentate chelation of catechol group with Ti 4+ and then acts as both an anchor and a reducer to in situ nucleate and grow Ag nanocrystals on the TNT surface. By adjusting the AgNO 3 concentration, the loading amount of Ag nanocrystals on the TNT surface can be controlled easily, and the visible-light absorption ability of Ag/TNT heterojunctions enhances with increasing the Ag loading amount. Moreover, their photocatalytic activity was evaluated by the degradation capability of Rhodamine B (RhB) under visible light. The Ag/ TNT heterojunctions exhibit the high visible-light photocatalytic activity, which can almost degrade 100% RhB within 2 h. This excellent performance can be attributed to the local electric field caused by the surface plasmon resonance (SPR) of Ag nanocrystals and the high adsorption capability of TNTs with large specific surface area.

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Coupled cluster CCSD(T) calculations with core-valence correlation and complete basis set (CBS) limit extrapolation are used to benchmark the performance of commonly used density functionals in computing energy barriers for Zr-mediated reactions involving zirconocene species. These reactions include (a) insertions of the Zr-H bond of Cp2Zr(H)Cl into C═C, C≡C, and C═O bonds and (b) C-H activations by Zr═N bond in Cp2Zr═NH. The best performing functionals are M06-L, M06, and M06-2X in the M06 series, all having mean unsigned deviations (MUD) less than 2 kcal/mol. The worst performing functional is OLYP, with a distinctly large MUD of more than 10 kcal/mol. Considering also the trends in barrier heights and the systematic barrier height deviation, our best recommended functional is M06-2X. In this work, DFT empirical dispersion correction (DFT-D3) is found to improve the performance of barrier height values for most functionals (especially of OLYP and B3LYP). With DFT empirical dispersion correction, we also recommend M06-2X for reaction barrier calculations of Zr-mediated reactions.

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