1 Solar conversion of carbon dioxide and water to value-added chemicals remains a challenge. A 2 number of solar-active catalysts have been reported but still suffer from low selectivity, poor 3 energy efficiency, and instability, and fail to drive simultaneous water oxidation. Herein, we 4 report CuFeO 2 and CuO mixed p-type catalysts fabricated via a widely employed electroplating 5 of earth-abundant cupric and ferric ions followed by annealing under atmospheric air. The 6 composite electrodes exhibited onset potentials at +0.9 V vs. RHE in CO 2 -purged bicarbonate 7 solution and converted CO 2 to formate with over 90% selectivity under simulated solar light (Air 8 Mass 1.5, 100 mW⋅cm −2 ). Wired CuFeO 2 /CuO photocathode and Pt anode couples produced 9 formate over 1 week at a solar-to-formate energy conversion efficiency of ~1% (selectivity 10 >90%) without any external bias while O 2 was evolved from water. Isotope and nuclear magnetic 11 resonance analyses confirmed the simultaneous production of formate and O 2 at the stand-alone 12 couples. Solar CO 2 recycling has received wide attention primarily to address global CO 2 emission and to 1 convert CO 2 and water to value-added chemicals. 1-3 Despite a long research history over the past 2 four decades, 4,5 the technology remains in an early stage, with low CO 2 conversion efficiency 3 and selectivity. CO 2 is highly stable and has limited solubility in water, and its reduction requires 4 multiple proton-coupled electron transfers, resulting in a range of carbon intermediates (C1 -5 C3) 2,6 as well as a larger amount of H 2 over CO 2 conversion products. 7-9 6 For the realization of solar CO 2 recycling, the system of interest should be operated 7 sustainably, which requires the development of not only energy-efficient and cost-effective 8 materials but also stand-alone, complete reaction processes (CO 2 reduction and water oxidation) 9 operating for long periods without any external bias. 10-12 A range of semiconductors (mostly p-10 types) have been studied for CO 2 conversion, including GaP, 4 InP, 5 GaAs, 13 Si, 8,14 Cu 2 O, 15-18 and 11 CuFeO 2 , 19,20 all of which have narrow bandgaps (E g ) and sufficient Fermi levels (E F ) capable of 12 reducing CO 2 . Although promising, these materials inherently require potential biases to drive 13 the CO 2 reduction reaction and compete with other metallic electrodes, 21 whereas complete 14 reactions (CO 2 reduction and water oxidation) have been rarely demonstrated due to large 15 overpotentials. Photocathode-photoanode couples have been demonstrated to operate, 11 yet the 16 syntheses of materials are complicated and the energy conversion efficiency is low (max. 0.14%). 17 We have searched for high-efficiency, low-cost, and scalable p-type materials and found 18 that CuFeO 2 and CuO mixed materials meet all requirements. To our surprise, this material 19 converted CO 2 to formate with selectivity greater than 90% over 1 week and simultaneously 20 produced molecular oxygen via water oxidation when simply ...

Photocatalytic water splitting is a sustainable technology for the production of clean fuel in terms of hydrogen (H2). In the present study, hydrogen (H2) production efficiency of three promising photocatalysts (titania (TiO2-P25), graphitic carbon nitride (g-C3N4), and cadmium sulfide (CdS)) was evaluated in detail using various sacrificial agents. The effect of most commonly used sacrificial agents in the recent years, such as methanol, ethanol, isopropanol, ethylene glycol, glycerol, lactic acid, glucose, sodium sulfide, sodium sulfite, sodium sulfide/sodium sulfite mixture, and triethanolamine, were evaluated on TiO2-P25, g-C3N4, and CdS. H2 production experiments were carried out under simulated solar light irradiation in an immersion type photo-reactor. All the experiments were performed without any noble metal co-catalyst. Moreover, photolysis experiments were executed to study the H2 generation in the absence of a catalyst. The results were discussed specifically in terms of chemical reactions, pH of the reaction medium, hydroxyl groups, alpha hydrogen, and carbon chain length of sacrificial agents. The results revealed that glucose and glycerol are the most suitable sacrificial agents for an oxide photocatalyst. Triethanolamine is the ideal sacrificial agent for carbon and sulfide photocatalyst. A remarkable amount of H2 was produced from the photolysis of sodium sulfide and sodium sulfide/sodium sulfite mixture without any photocatalyst. The findings of this study would be highly beneficial for the selection of sacrificial agents for a particular photocatalyst.

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The immobilization of molecular switches within materials can give rise to new bulk properties that are useful for a variety of applications.

A new class of treatment processes called advanced reduction processes (ARPs) is proposed. ARPs combine activation methods and reducing agents to form highly reactive reducing radicals that degrade oxidized contaminants. Batch screening experiments were conducted to identify effective ARPs by applying several combinations of activation methods (ultraviolet light, ultrasound, electron beam, and microwaves) and reducing agents (dithionite, sulfite, ferrous iron, and sulfide) to degradation of four target contaminants (perchlorate, nitrate, perfluorooctanoic acid, and 2,4 dichlorophenol) at three pH-levels (2.4, 7.0, and 11.2). These experiments identified the combination of sulfite activated by ultraviolet light produced by a low-pressure mercury vapor lamp (UV-L) as an effective ARP. More detailed kinetic experiments were conducted with nitrate and perchlorate as target compounds, and nitrate was found to degrade more rapidly than perchlorate. Effectiveness of the UV-L/sulfite treatment process improved with increasing pH for both perchlorate and nitrate. We present the theory behind ARPs, identify potential ARPs, demonstrate their effectiveness against a wide range of contaminants, and provide basic experimental evidence in support of the fundamental hypothesis for ARP, namely, that activation methods can be applied to reductants to form reducing radicals that degrade oxidized contaminants. This article provides an introduction to ARPs along with sufficient data to identify potentially effective ARPs and the target compounds these ARPs will be most effective in destroying. Further research will provide a detailed analysis of degradation kinetics and the mechanisms of contaminant destruction in an ARP.