One-Step High-Temperature Electrodeposition of Fe-Based Films as Efficient Water Oxidation Catalysts.

Electrolysis of water to produce hydrogen requires an efficient catalyst preferably made of cheap and abundant metal ions for the improved water oxidation reaction. An Fe-based film has been deposited in a single step by electrochemical deposition at temperatures higher than the room temperature. Until now, the electrodeposition of iron oxide has been carried out at 298 K or at lower temperatures under a controlled atmosphere to prohibit atmospheric oxidation of Fe2+ of the iron precursor. A metal inorganic complex, ferrocene, and non-aqueous electrolyte medium propylene carbonate have been used to achieve electrodeposition of iron oxide without the need of any inert or controlled atmosphere. At 298 K, the amorphous film was formed, whereas at 313 K and at higher temperatures, the hematite film was grown, as confirmed by X-ray diffraction. The transformation of iron of the ferrocene into a higher oxidation state under the experimental conditions used was further confirmed by X-ray photoelectron spectroscopy, ultraviolet-visible, and electron paramagnetic resonance spectroscopic methods. The films deposited at 313 K showed the best performance for water oxidation with remarkable long-term electrocatalytic stability and an impressive turnover frequency of 0.028 s-1 which was 4.5 times higher than that of films deposited at 298 K (0.006 s-1). The observed overpotential to achieve a current density of 10 mA cm-2 was found to be 100 mV less for the film deposited at 313 K compared to room-temperature-derived films under similar experimental conditions. Furthermore, electrochemical impedance data revealed that films obtained at 313 K have the least charge transfer resistance (114 Ω) among all, supporting the most efficient electron transport in the film. To the best of our knowledge, this is the first-ever report where the crystalline iron-based film has been shown to be electrodeposited without any post-deposition additional treatment for alkaline oxygen evolution reaction application.

Advanced nanomaterials for highly efficient CO2 photoreduction and photocatalytic hydrogen evolution.

At present, CO2 photoreduction to value-added chemicals/fuels and photocatalytic hydrogen generation by water splitting are the most promising reactions to fix two main issues simultaneously, rising CO2 levels and never-lasting energy demand. CO2, a major contributor to greenhouse gases (GHGs) with about 65% of the total emission, is known to cause adverse effects like global temperature change, ocean acidification, greenhouse effects, etc. The idea of CO2 capture and its conversion to hydrocarbons can control the further rise of CO2 levels and help in producing alternative fuels that have several further applications. On the other hand, hydrogen being a zero-emission fuel is considered as a clean and sustainable form of energy that holds great promise for various industrial applications. The current review focuses on the discussion of the recent progress made in designing efficient photocatalytic materials for CO2 photoreduction and hydrogen evolution reaction (HER). The scope of the current study is limited to the TiO2 and non-TiO2 based advanced nanomaterials (i.e. metal chalcogenides, MOFs, carbon nitrides, single-atom catalysts, and low-dimensional nanomaterials). In detail, the influence of important factors that affect the performance of these photocatalysts towards CO2 photoreduction and HER is reviewed. Special attention is also given in this review to provide a brief account of CO2 adsorption modes on the catalyst surface and its subsequent reduction pathways/product selectivity. Finally, the review is concluded with additional outlooks regarding upcoming research on promising nanomaterials and reactor design strategies for increasing the efficiency of the photoreactions.

Investigation of Li-rich manganese oxide spinel structures for electrochemical water oxidation catalysis.

The rapid development of efficient and cost-effective catalysts is essential for the oxygen evolution reaction. Herein, nanostructured spinels LiMn2O4, delithiated λ-MnO2, and Li4Mn5O12 have been synthesized at low temperatures and are investigated as electrocatalysts for alkaline water oxidation reactions. Among the nanostructured spinels, LiMn2O4, delithiated λ-MnO2, and Li4Mn5O12, the former spinel which is classical LiMn2O4 with 1/6th of the Mn replaced by Li outperforms for the OER that shows a current density of 5 mA cm-2 at a lowest overpotential of 430 mV and Tafel slope of 74 mV per decade. Electrochemical impedance studies revealed the least value of charge transfer resistance of the Li4Mn5O12 spinel and suggest fast reaction kinetics for the oxygen evolution reaction as compared to other spinels. The XPS and TEM of Li4Mn5O12, recorded after a 12-hour stability test for oxygen evolution activity, confirm that the oxidation state of Mn and the morphology of Li4Mn5O12 remain intact even after the electrocatalytic reaction, however, it undergoes amorphization. The higher activity of Li4Mn5O12 synthesized in the present work is attributed to the low temperature synthesis resulting in the formation of a nanostructured Li rich spinel with a high surface area, along with an increased percentage of ionic bonding and the presence of 3D Li diffusion channels. The role of Li was further supported by XPS studies that revealed a shift in Li 1s binding energy as well as quantitative reduction relative to Mn for Li4Mn5O12 after a long term test.