Search

A synthetic method for uniform and pure Cs3Sb2Br9 NCs has been developed. Cs3Sb2Br9 NCs exhibit a 10-fold increase in activity for the photocatalytic CO2 reduction reaction compared to CsPbBr3 NCs, achieving 510 μmol CO g-1 cat. after 4 h. Density functional theory shows that Cs3Sb2Br9 surfaces sufficiently expose Sb to allow reactivity, as opposed to the unreactive CsPbBr3 surface.

Correction for ‘Synthesis of lead-free Cs3Sb2Br9 perovskite alternative nanocrystals with enhanced photocatalytic CO2 reduction activity’ by Chang Lu et al., Nanoscale, 2020, 12, 2987–2991, https://doi.org/10.1039/C9NR07722G.

A family of solid solutions, Cu5(Ta1- xNb x)11O30 (0 ≤ x ≤ 0.4), was investigated as p-type semiconductors for their band gaps and energies and for their activity for the reduction of water to molecular hydrogen. Compositions from 0 to 40 mol % niobium were prepared in high purity by solid-state methods, accompanied by only very small increases in the lattice parameters of ∼0.05% and with the niobium and tantalum cations disordered over the same atomic sites. However, an increasing niobium content causes a significant decrease in the bandgap size from ∼2.58 to ∼2.05 eV owing to the decreasing conduction band energies. Linear-sweep voltammetry showed an increase in cathodic photocurrents with niobium content and applied negative potential of up to -0.6 mA/cm2 (pH ∼7.3; AM 1.5 G light filter with an irradiation intensity of ∼100 mW/cm2). The cathodic photocurrents could be partially stabilized by heating the polycrystalline films in air at 550 °C for 1 h to produce surface nanoislands of CuO or using protecting layers of aluminum-doped zinc oxide and titania. Aqueous suspensions of the Cu5(Ta1- xNb x)11O30 powders were also found to be active for hydrogen production under visible-light irradiation in a 20% aqueous methanol solution with the highest apparent quantum yields for the 10% and 20% Nb-substituted samples. Electronic structure calculations show that the increased photocurrents and hydroen evolution activities of the solid solutions arise near the percolation threshold of the niobate/tantalate framework wherein the Nb cations establish an extended -O-Nb-O-Nb-O- diffusion pathway for the minority carriers. The latter also reveals a novel pathway for enhancing charge separation as a function of the niobium-oxide connectivity. Thus, these results illustrate the advantages of using solid solutions to achieve the smaller bandgap sizes and band energies that are needed for solar-driven photocatalytic reactions.

In the colloidal synthesis of inorganic perovskite materials, cesium oleate (CsOL) is the most commonly used Cs precursor. Yet, despite its ubiquitous use in literature, CsOL has been observed to be insoluble at room temperature and leads to surprisingly inconsistent results in CsPbX3 nanocrystal synthesis, depending on the Cs salt from which the precursor is derived. We show that under the conditions used in most reports, the amount of oleic acid (OA) added, while stoichiometrically sufficient, still leads to incomplete conversion of the Cs salts to CsOL. This results in a mixture of Cs sources being present during the reaction, causing decreased homogeneity and reproducibility. When a 1:5 Cs:OA ratio is used, complete conversion is readily obtained, even under mild conditions, resulting in a precursor solution that is soluble at room temperature and yields identical synthetic results, regardless of the initial Cs source. Furthermore, 1H nuclear magnetic resonance (NMR) of solutions prepared using varyin...

Despite progress in small scale electrocatalytic production of hydrogen peroxide (H2O2) using a rotating ring-disk electrode, further work is needed to develop a non-toxic, selective, and stable O2-to-H2O2 electrocatalyst for realizing continuous on-site production of neutral hydrogen peroxide. We report ultrasmall and monodisperse colloidal PtP2 nanocrystals that achieve H2O2 production at near zero-overpotential with near unity H2O2 selectivity at 0.27 V vs. RHE. Density functional theory calculations indicate that P promotes hydrogenation of OOH* to H2O2 by weakening the Pt-OOH* bond and suppressing the dissociative OOH* to O* pathway. Atomic layer deposition of Al2O3 prevents NC aggregation and enables application in a polymer electrolyte membrane fuel cell (PEMFC) with a maximum r(H2O2) of 2.26 mmol h−1 cm−2 and a current efficiency of 78.8% even at a high current density of 150 mA cm−2. Catalyst stability enables an accumulated neutral H2O2 concentration in 600 mL of 3.0 wt% (pH = 6.6)., The synthesis of high concentration H2O2 from water and oxygen at moderate conditions could provide an on-site H2O2 source for medical and water purification applications. Here, authors show Al2O3-stabilized PtP2 nanocrystals to enable selective, stable and efficient neutral pH H2O2 production.

A synthetic method for uniform and pure Cs3Sb2Br9 NCs has been developed. Cs3Sb2Br9 NCs exhibit a 10-fold increase in activity for the photocatalytic CO2 reduction reaction compared to CsPbBr3 NCs, achieving 510 μmol CO g-1 cat. after 4 h. Density functional theory shows that Cs3Sb2Br9 surfaces sufficiently expose Sb to allow reactivity, as opposed to the unreactive CsPbBr3 surface.

Colloidal semiconductor quantum dot (CQD)-based photocathodes for solar-driven hydrogen evolution have attracted significant attention because of their tunable size, nanostructured morphology, crystalline orientation, and band gap. Here, we report a thin film heterojunction photocathode composed of organic PEDOT:PSS as a hole transport layer, CdSe CQDs as a semiconductor light absorber, and conformal Pt layer deposited by atomic layer deposition (ALD) serving as both a passivation layer and cocatalyst for hydrogen evolution. In neutral aqueous solution, a PEDOT:PSS/CdSe/Pt heterogeneous photocathode with 200 cycles of ALD Pt produces a photocurrent density of −1.08 mA/cm2 (AM-1.5G, 100 mW/cm2) at a potential of 0 V versus reversible hydrogen electrode (RHE) (j0) in neutral aqueous solution, which is nearly 12 times that of the pristine CdSe photocathode. This composite photocathode shows an onset potential for water reduction at +0.46 V versus RHE and long-term stability with negligible degradation. In th...

Developing earth-abundant and efficient electrocatalysts for photoelectrochemical water splitting is critical to realizing a high-performance solar-to-hydrogen energy conversion process. Herein, phosphorus-rich colloidal cobalt diphosphide nanocrystals (CoP

Highly efficient and stable electrocatalysts, particularly those that are capable of multifunctionality in the same electrolyte, are in high demand for the hydrogen evolution reaction (HER), oxygen evolution reaction (OER), and oxygen reduction reaction (ORR). In this work, highly monodisperse CoP and Co2 P nanocrystals (NCs) are synthesized using a robust solution-phase method. The highly exposed (211) crystal plane and abundant surface phosphide atoms make the CoP NCs efficient catalysts toward ORR and HER, while metal-rich Co2 P NCs show higher OER performance owing to easier formation of plentiful Co2 P@COOH heterojunctions. Density functional theory calculation results indicate that the desorption of OH* from cobalt sites is the rate-limiting step for both CoP and Co2 P in ORR and that the high content of phosphide can lower the reaction barrier. A water electrolyzer constructed with a CoP NC cathode and a Co2 P NC anode can achieve a current density of 10 mA cm-2 at 1.56 V, comparable even to the noble metal-based Pt/C and RuO2 /C pair. Furthermore, the CoP NCs are employed as an air cathode in a primary zinc-air battery, exhibiting a high power density of 62 mW cm-2 and good stability.

Developing earth-abundant and efficient electrocatalysts for photoelectrochemical water splitting is critical to realizing a high-performance solar-to-hydrogen energy conversion process. Herein, phosphorus-rich colloidal cobalt diphosphide nanocrystals (CoP2 NCs) are synthesized via hot injection. The CoP2 NCs show a Pt-like hydrogen evolution reaction (HER) electrocatalytic activity in acidic solution with a small overpotential of 39 mV to achieve -10 mA cm-2 and a very low Tafel slope of 32 mV dec-1 . Density functional theory (DFT) calculations reveal that the high P content both physically separates Co atoms to prevent H from over binding to multiple Co atoms, while simultaneously stabilizing H adsorbed to single Co atoms. The catalytic performance of the CoP2 NCs is further demonstrated in a metal-insulator-semiconductor photoelectrochemical device consisting of bottom p-Si light absorber, atomic layer deposition Al-ZnO passivation layers, and the CoP2 cocatalyst. The p-Si/AZO/TiO2 /CoP2 photocathode shows a photocurrent density of -16.7 mA cm-2 at 0 V versus reversible hydrogen electrode (RHE) and an output photovoltage of 0.54 V. The high performance and stability are attributed to the junction between p-Si and AZO, the corrosion-resistance of the pinhole-free TiO2 protective layer, and the fast HER kinetics of the CoP2 NCs.