Development of Double Perovskite Oxide Photocatalysts for Efficient Visible-Light Driven Photocatalytic Water Splitting and CO2 Reduction

Abstract

Energy and environment are the key global challenges in the 21st century. Solar energy is considered the most promising clean and sustainable energy resource due to its university, inexhaustible and environmental friendliness. One of the most viable means of solar energy conversion and utilization is artificially converting solar energy into chemical energy as natural photosynthesis does. H2 produced from water splitting and CO2 reduction, are the major research topics of artificial photosynthesis. However, the effective conversion of solar energy into chemical energy by cost-effective artificial means on a large scale remains elusive. Metal oxide-based photocatalysts are the most studied materials for photocatalytic water splitting and CO2 reduction. Particularly, perovskite oxides with the chemical formula of ABO3 have been intensively studied as semiconductor photocatalysts. However, overwhelmingly of the perovskite oxides are only active under UV-light-irradiation, which limited their potential in solar energy application. Therefore, breakthrough technology and step-change materials, particularly, visible-light-responsive photocatalysts are highly desirable for the development of photocatalytic systems. In recent years, copious progress has been made in designing materials that function under visible-light-irradiation. So far, the most successful strategy is anion doping of oxide semiconductors, such as nitrogen or sulfur dope to form oxynitrides and oxysulfides, respectively. For example, nitrogen-doped oxynitrides such as (Ga1-xZnx)(N1-xOx) and ANbO2N (A=Sr, Ba, and La)1, and sulfur-doped oxysulfides such as Sm2Ti2S2O5 2 showed efficient photocatalytic overall water splitting activities under visible-light-irradiation. Particularly, oxynitrides (Ga1-xZnx)(N1-xOx) based photocatalyst sheet, showed remarkable photocatalytic overall water splitting activity with AQE of more than 30% at l»420 nm3. However, these oxynitrides and oxysulfides suffer stability problems due to photocorrosion, hindering their potential practical application in photocatalytic applications. Recently, it has been theorized that double perovskite oxides (DPOs) with the chemical formula of A2BʹB"O6 can function as efficient and stable visible-light-responsive photocatalysts for photocatalytic water splitting and CO2 reduction. However, DPOs have been rarely studied for photocatalytic water splitting and CO2 reduction due to the difficulty of obtaining pure phase materials and the paucity of exposed active sites. Thus, developing efficient and stable visible-light-responsive DPOs photocatalysts for photocatalytic water splitting and CO2 reduction becomes important. In this regard, recently, we have demonstrated a series of efficient and stable visible-light-responsive DPOs photocatalysts for photocatalytic water splitting. For instance, Sr2CoWO6 and Sr2CoTaO6 can serve as an efficient and stable bifunctional photocatalyst for both photocatalytic oxygen evolution reaction (OER) and hydrogen evolution reaction(HER)4, 5, and Sr2NiWO6 can efficiently drive the photocatalytic OER6. Even though these DPOs have been demonstrated as visible-light-responsive photocatalysts with suitable CB and VB positions that straddle the theoretical potentials for overall water splitting, however, one-step overall water splitting has not been achieved so far, and their potential for photocatalytic CO2 reduction has not been studied yet. Overall water splitting under visible-light-irradiation based on particulate photocatalysts is a challenging reaction, which is regarded as one of the “Holy Grail” of sciences. And oxide semiconductors showing both photocatalytic OER and HER activities are rare. Nevertheless, bifunctional photocatalytic OER and HER were successfully demonstrated based on Sr2CoWO6 and Sr2CoTaO6. Further improvement of the material designs and developing appropriate cocatalysts may play a key role in achieving one-step overall water splitting under visible-light-irradiation based on DPOs photocatalysts. This work is mainly to explore the possibility of utilizing DPOs materials as visible-light-responsive photocatalysts for photocatalytic water splitting and CO2 reduction reaction, which is challenging work but has great potential value in advancing science and technology in photocatalysis. We anticipated that this work will provide a novel and rational strategy for improving the light absorption, charge separation and charge utilization in DPOs photocatalysts. References Maeda, K.; Teramura, K.; Masuda, H.; Takata, T.; Saito, N.; Inoue, Y.; Domen, K. 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