The effect of crystallinity on photocatalytic performance of Co3O4 water-splitting cocatalysts.

Cocatalysts, when loaded onto a water splitting photocatalyst, accelerate the gas evolution reaction and improve the efficiency of the photocatalyst. In this paper, we report that the efficiency of the photocatalyst is enhanced using an amorphous cobalt oxide cocatalyst. The WO3 film, when loaded with amorphous or nanocrystalline Co3O4, shows an improvement of up to 40% in photocurrent generation and 34% in hydrogen gas evolution. The effect of cocatalyst crystallinity on performance was systematically studied, and we found that the photocurrent deteriorates with the conversion of the cocatalyst to a highly crystalline phase at an annealing temperature of 500 °C. The mechanism of this effect was studied in detail using electrochemical impedance spectroscopy, and the enhancement effect produced by the amorphous cocatalyst is attributed to the large density of unsaturated catalytically active sites in the amorphous material.

Sol-gel deposited Cu2O and CuO thin films for photocatalytic water splitting.

Cu2O and CuO are attractive photocatalytic materials for water splitting due to their earth abundance and low cost. In this paper, we report the deposition of Cu2O and CuO thin films by a sol-gel spin-coating process. Sol-gel deposition has distinctive advantages such as low-cost solution processing and uniform film formation over large areas with a precise stoichiometry and thickness control. Pure-phase Cu2O and CuO films were obtained by thermal annealing at 500 °C in nitrogen and ambient air, respectively. The films were successfully incorporated as photocathodes in a photoelectrochemical (PEC) cell, achieving photocurrents of -0.28 mA cm(-2) and -0.35 mA cm(-2) (for Cu2O and CuO, respectively) at 0.05 V vs. a reversible hydrogen electrode (RHE). The Cu2O photocurrent was enhanced to -0.47 mA cm(-2) upon incorporation of a thin layer of a NiOx co-catalyst. Preliminary stability studies indicate that CuO may be more stable than Cu2O as a photocathode for PEC water-splitting.

Nanoengineered Advanced Materials for Enabling Hydrogen Economy: Functionalized Graphene-Incorporated Cupric Oxide Catalyst for Efficient Solar Hydrogen Production.

Cupric oxide (CuO) is a promising candidate as a photocathode for visible-light-driven photo-electrochemical (PEC) water splitting. However, the stability of the CuO photocathode against photo-corrosion is crucial for developing CuO-based PEC cells. This study demonstrates a stable and efficient photocathode through the introduction of graphene into CuO film (CuO:G). The CuO:G composite electrodes are prepared using graphene-incorporated CuO sol-gel solution via spin-coating techniques. The graphene is modified with two different types of functional groups, such as amine (-NH2) and carboxylic acid (-COOH). The -COOH-functionalized graphene incorporation into CuO photocathode exhibits better stability and also improves the photocurrent generation compare to control CuO electrode. In addition, -COOH-functionalized graphene reduces the conversion of CuO phase into cuprous oxide (Cu2O) during photo-electrochemical reaction due to effective charge transfer and leads to a more stable photocathode. The reduction of CuO to Cu2O phase is significantly lesser in CuO:G-COOH as compared to CuO and CuO:G-NH2 photocathodes. The photocatalytic degradation of methylene blue (MB) by CuO, CuO:G-NH2 and CuO:G-COOH is also investigated. By integrating CuO:G-COOH photocathode with a sol-gel-deposited TiO2 protecting layer and Au-Pd nanostructure, stable and efficient photocathode are developed for solar hydrogen generation.

Stable and Efficient CuO Based Photocathode through Oxygen-Rich Composition and Au-Pd Nanostructure Incorporation for Solar-Hydrogen Production.

Enhancing stability against photocorrosion and improving photocurrent response are the main challenges toward the development of cupric oxide (CuO) based photocathodes for solar-driven hydrogen production. In this paper, stable and efficient CuO-photocathodes have been developed using in situ materials engineering and through gold-palladium (Au-Pd) nanoparticles deposition on the CuO surface. The CuO photocathode exhibits a photocurrent generation of ∼3 mA/cm2 at 0 V v/s RHE. Time-of-flight secondary ion mass spectrometry (TOF-SIMS) analysis and X-ray spectroscopy (XPS) confirm the formation of oxygen-rich (O-rich) CuO film which demonstrates a highly stable photocathode with retained photocurrent of ∼90% for 20 min. The influence of chemical composition on the photocathode performance and stability has been discussed in detail. In addition, O-rich CuO photocathodes deposited with Au-Pd nanostructures have shown enhanced photoelectrochemical performance. Linear scan voltammetry characteristic shows ∼25% enhancement in photocurrent after Au-Pd deposition and reaches ∼4 mA/cm2 at "0" V v/s RHE. Hydrogen evolution rate significantly depends on the elemental composition of CuO and metal nanostructure. The present work has demonstrated a stable photocathode with high photocurrent for visible-light-driven water splitting and hydrogen production.

Nanocrystal Engineering of Sputter-Grown CuO Photocathode for Visible-Light-Driven Electrochemical Water Splitting.

Cupric oxide (CuO) thin film was sputtered onto fluorine-doped tin oxide (FTO) coated glass substrate and incorporated into a photoelectrochemical (PEC) cell as a photocathode. Through in situ nanocrystal engineering, sputtered CuO film shows an improvement in its stability and photocurrent generation capability. For the same CuO film thickness (150 nm), films deposited at a sputtering power of 300 W exhibit a photocurrent of ∼0.92 mAcm(-2) (0 V vs RHE), which is significantly higher than those deposited at 30 W (∼0.58 mAcm(-2)). By increasing the film thickness to 500 nm, the photocurrent is further enhanced to 2.5 mAcm(-2), which represents a photocurrent conversion efficiency of 3.1%. Systematic characterization using Raman, XRD, and HR-TEM reveals that the high sputtering power results in an improvement in CuO film crystallinity, which enhances its charge transport property and, hence, its photocurrent generation capabilities.