Electrocatalytic water splitting to produce hydrogen comprises the hydrogen and oxygen evolution half reactions (HER and OER), with the latter as the bottleneck process. Thus, enhancing the OER performance and understanding the mechanism are critically important. Herein, we report a strategy for OER enhancement by utilizing gold nanoclusters to form cluster/CoSe composites; the latter exhibit largely enhanced OER activity in alkaline solutions. The Au/CoSe composite affords a current density of 10 mA cm at small overpotential of ∼0.43 V (cf. CoSe: ∼0.52 V). The ligand and gold cluster size can also tune the catalytic performance of the composites. Based upon XPS analysis and DFT simulations, we attribute the activity enhancement to electronic interactions between nanocluster and CoSe, which favors the formation of the important intermediate (OOH) as well as the desorption of oxygen molecules over Au/CoSe composites in the process of water oxidation. Such an atomic level understanding may provide some guidelines for design of OER catalysts.
To explore the electronic and catalytic properties of nanoclusters, here we report an aromatic-thiolate-protected gold nanocluster, [Au25(SNap)18](-) [TOA](+), where SNap = 1-naphthalenethiolate and TOA = tetraoctylammonium. It exhibits distinct differences in electronic and catalytic properties in comparison with the previously reported [Au25(SCH2CH2Ph)18](-), albeit their skeletons (i.e., Au25S18 framework) are similar. A red shift by ∼10 nm in the HOMO-LUMO electronic absorption peak wavelength is observed for the aromatic-thiolate-protected nanocluster, which is attributed to its dilated Au13 kernel. The unsupported [Au25(SNap)18](-) nanoclusters show high thermal and antioxidation stabilities (e.g., at 80 °C in the present of O2, excess H2O2, or TBHP) due to the effects of aromatic ligands on stabilization of the nanocluster's frontier orbitals (HOMO and LUMO). Furthermore, the catalytic activity of the supported Au25(SR)18/CeO2 (R = Nap, Ph, CH2CH2Ph, and n-C6H13) is examined in the Ullmann heterocoupling reaction between 4-methyl-iodobenzene and 4-nitro-iodobenzene. Results show that the activity and selectivity of the catalysts are largely influenced by the chemical nature of the protecting thiolate ligands. This study highlights that the aromatic ligands not only lead to a higher conversion in catalytic reaction but also markedly increase the yield of the heterocoupling product (4-methyl-4'-nitro-1,1'-biphenyl). Through a combined approach of experiment and theory, this study sheds light on the structure-activity relationships of the Au25 nanoclusters and also offers guidelines for tailoring nanocluster properties by ligand engineering for specific applications.
The two-electron water oxidation reaction (2e-WOR) is a promising route for distributed electrochemical synthesis of hydrogen peroxide (H 2 O 2 ), an effective and green oxidizer, bleaching agent, and antiseptic. To date, the best electrocatalyst for 2e-WOR, in terms of selectivity against the competing 4e-WOR to form O 2 , is BiVO 4 . Nevertheless, BiVO 4 is unstable and has a high overpotential of ∼340 mV at 0.2 mA/cm 2 for 2e-WOR. Herein, we use density functional theory to identify a new, efficient, selective, and stable electrocatalyst for 2e-WOR, i.e., the ternary oxide calcium stannate (CaSnO 3 ). Our experiments show that CaSnO 3 achieves an overpotential of 230 mV at 0.2 mA/cm 2 , peak Faraday efficiency of 76% for 2e-WOR at 3.2 V vs the reversible hydrogen electrode (RHE), and stable performance for over 12 h, outperforming BiVO 4 in all aspects. This work demonstrates the promise of CaSnO 3 as a selective and cost-effective electrocatalyst candidate for H 2 O 2 production from water oxidation.
Silicon nanoparticles (NPs) have been widely accepted as an alternative material for typical quantum dots and commercial organic dyes in light-emitting and bioimaging applications owing to silicon's intrinsic merits of least toxicity, low cost, and high abundance. However, to date, how to improve Si nanoparticle photoluminescence (PL) performance (such as ultrahigh quantum yield, sharp emission peak, high stability) is still a major issue. Herein, we report surface nitrogen-capped Si NPs with PL quantum yield up to 90% and narrow PL bandwidth (full width at half-maximum (fwhm) ≈ 40 nm), which can compete with commercial dyes and typical quantum dots. Comprehensive studies have been conducted to unveil the influence of particle size, structure, and amount of surface ligand on the PL of Si NPs. Especially, a general ligand-structure-based PL energy law for surface nitrogen-capped Si NPs is identified in both experimental and theoretical analyses, and the underlying PL mechanisms are further discussed.
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