Photodeposited CoOx as highly active phases to boost water oxidation on BiVO4/WO3 photoanode

Surface decoration of photoanodes with oxygen evolution cocatalysts is an efficient approach to improve the photoelectrochemical water splitting performance. Herein, ultrafine CoO_x was selectively immobilized on the surface of BiVO₄/WO₃ photoanode by using the photogenerated holes to in-situ oxidize Co₄O₄ cubane. The composited photoanode (CoO_x/BiVO₄/WO₃) displayed an enhanced photoelectrochemical (PEC) water oxidation performance, with a photocurrent density of 2.3 mA/cm² at 1.23 V_RHE under the simulated sunlight irradiation, which was 2 times higher than that of bare BiVO₄/WO₃. The characterization results for the morphological, optical and electrochemical properties of the photoelectrodes revealed that, the enhanced PEC performances could be attributed to the improved charge carrier separation/transport behaviors and the promoted water oxidation kinetics when the photoelectrodes were loaded with CoO_x.     

Multidisciplinary methods (co-precipitation,ultrasonic, microwave,reflux and hydrothermal) for synthesis and characterization of CaMn3O6 nanostructures and its photocatalytic water splitting performance

Production of hydrogen and oxygen from water splitting reaction under visible light is a simple method for conversion of solar-to-hydrogen energy and it is a hopeful clean and renewable method for H₂ fuel generation. However, there is still a lack of potential materials with significant activity under visible light. Because of safety, chemical inertness, low cost, stability and other characteristics, transition metal oxide semiconductors have been widely applied as photocatalysts for hydrogen generation. Albeit, wide usage of semiconductor photocatalysts were prevented by its inability to exploit solar energy of visible region. Here we show synthesis of a nano-sized mixed metal oxide (MMO) Ca₃MnO₆ through wet-chemistry methods such as co-precipitation, ultrasonic, microwave, reflux, and hydrothermal methods. The nano-sized Ca₃MnO₆ has initially selected based on morphology and respective particle diameters. The selected sample shows a well-defined single crystal, free from any impurities, complete structural formation, and a band gap energy (E_g) of around 5.3 eV. The best product synthesized in ultrasonic method which shows the best morphology, purity and the highest efficiency for splitting of water to hydrogen and oxygen. Irrespective of preparation methods and morphologies, all samples split water into hydrogen and oxygen, as confirmed from their respective photocatalytic analysis. When the selected sample combined with (NH₄)₂Ce(NO₃)₆, the single-crystal Ca₃MnO₆ nanoparticles split water into hydrogen and oxygen more efficiently under visible light. Our findings demonstrate the importance of nanostructured Ca₃MnO₆ single-crystal photocatalysts in solar water splitting.     

High-efficiency photoelectrochemical water splitting with heterojunction photoanode of In2O3-x nanorods/black Ti–Si–O nanotubes

Constructing heterojunction was an efficient way to promote photoelectrochemical (PEC) water splitting performance of TiO₂-based nano-photoanode. In this work, we demonstrated the feasible preparation of oxygen vacancies-induced In₂O₃ (In₂O_3-x) nanorods/black Si-doped TiO₂ (Ti–Si–O) nanotubes heterojunction photoanode for enhanced PEC water splitting. Black Ti–Si–O nanotubes were fabricated through Zn reduction of the as-annealed Ti–Si–O nanotubes, followed by In₂O_3-x nanorods coupling by a facile electrodepositing and Ar heat treatment. Solar to hydrogen conversion efficiency of the heterojunction photoanode reached as high as 1.96%, which was almost 10 times that of undoped TiO₂. The improved PEC properties were mainly attributed to co-doping effects of Si and Ti³⁺/oxygen vacancy as well as In₂O_3-x decoration, which resulted in enhanced optical absorption and facilitated separation-transport process of photogenerated charge carriers. Charge transfer process in the composite system and hydrogen production mechanism were proposed. This work will facilitate designing TiO₂-based nano-photoanodes for promoting water splitting by integrating with elements doping, oxygen vacancies self-doping and semiconductors coupling.     

1D ZnFe2O4 nanorods coupled with plasmonic Ag,Ag2S nanoparticles and Co-Pi cocatalysts for efficient photoelectrochemical water splitting

Improving the absorption of visible light, accelerating the separation of carries and reducing the recombination of electron-hole pairs are critical to enhance photoelectrochemical (PEC) performance of ZnFe₂O₄. Herein, the ZnFe₂O₄/Ag/Ag₂S films are firstly prepared with a photocurrent density of 0.91 mA/cm² at 1.23 V vs. RHE, which is 9.10 times higher than that of pristine ZnFe₂O₄ (0.10 mA/cm² at 1.23 V vs. RHE). On the basis, Co-Pi cocatalyst is deposited on ZnFe₂O₄/Ag/Ag₂S to further optimize PEC performance of ZnFe₂O₄, the photocurrent density of ZnFe₂O₄/Ag/Ag₂S/Co-Pi is 1.18 mA/cm² at 1.23 V vs. RHE. The improved PEC performance of ZnFe₂O₄/Ag/Ag₂S/Co-Pi films could be attributed to: (i) fast transmission of electron-hole pairs owing to 1D ZnFe₂O₄ NRs; (ii) surface plasmon resonance (SPR) effect of Ag nanoparticles; (ⅲ) visible light absorption is improved by sensitization of Ag₂S nanoparticles; (ⅳ) Co-Pi cocatalyst decreases the recombination of electron-hole pairs by capturing holes. This work provides new insights for metal plasmas, sensitizers and cocatalysts synergistically modify photoanodes for efficient PEC water splitting.     

Unassisted water splitting with 9.3% efficiency by a single quantum nanostructure photoelectrode

To split water and produce hydrogen by white light is an excellent solution for the storage and supply of clean and sustainable energy. Efficiency and stability are the key challenges for a successful exploitation. InGaN, evaluated against other semiconductors, metal oxides, carbon based - and organic materials has most suited intrinsic materials properties. Based on this optimum materials choice we report photoelectrochemical (PEC) hydrogen generation under white light illumination by an InGaN-based quantum nanostructure photoelectrode. No degradation occurs for operation over 10 h. Our novel concept, combining quantum nanostructure physics with electrochemistry and catalysis leads to almost 10% efficiency at zero external voltage. The efficiency rises above 25% at 0.2 V. This is unmatched for a single photoelectrode, representing the most advanced technology of low complexity.     

A comprehensive review of hydrogen production and storage: A focus on the role of nanomaterials

Nanomaterials are beginning to play an essential role in addressing the challenges associated with hydrogen production and storage. The outstanding physicochemical properties of nanomaterials suggest their applications in almost all technological breakthroughs ranging from catalysis, metal-organic framework, complex hydrides, etc. This study outlines the applications of nanomaterials in hydrogen production (considering both thermochemical, biological, and water splitting methods) and storage. Recent advances in renewable hydrogen production methods are elucidated along with a comparison of different nanomaterials used to enhance renewable hydrogen production. Additionally, nanomaterials for solid-state hydrogen storage are reviewed. The characteristics of various nanomaterials for hydrogen storage are compared. Some nanomaterials discussed include carbon nanotubes, activated carbon, metal-doped carbon-based nanomaterials, metal-organic frameworks. Other materials such as complex hydrides and clathrates are outlined. Finally, future research perspectives related to the application of nanomaterials for hydrogen production and storage are discussed.     

Highly active Ni/Co-metal organic framework bifunctional electrocatalyst for water splitting reaction

Rational design of electrocatalycally active materials with excellent performance for renewable energy conversion is of great interest. We have developed a nanosheet array of Ni/Co metal-organic framework (MOF) grown on CoO modified Ni foam (CoO/NF) substrate via the solvothermal process. The high surface area and low resistance of Ni/Co-MOF@CoO/NF (NC@CoO/NF) catalyst contribute to efficient water splitting. We have prepared a series of NC-n/CoO/NF (n = 1–4) catalysts to optimize the molar ratio of the Co atom in Ni MOF-74. Among them, NC-2@CoO/NF shows an excellent electrochemical performance in alkaline medium, i.e., low overpotential of 290 and 139 mV for oxygen evolution reaction (OER) and hydrogen evolution reaction (HER), respectively. For a two-electrode system with NC-2@CoO/NF, a low cell voltage of 1.54 V at 10 mA cm^?2 has been obtained for overall water splitting which is much smaller than that with commercial Ir/C– Pt/C pair. This excellent performance can be attributed to the synergistic effects of Ni/Co-MOF and CoO/NF. In addition, the as-prepared NC-2@CoO/NF exhibits excellent long-term stability. The computational simulation also supports experimental results.     

A review of hydrogen production processes by photocatalytic water splitting – From atomistic catalysis design to optimal reactor engineering

‘Renewable energy is an essential part of our strategy of decarbonization, decentralization, as well as digitalization of energy.’ – Isabelle Kocher.Current climate, health and economic condition of our globe demands the use of renewable energy and the development of novel materials for the efficient generation, storage and transportation of renewable energy. Hydrogen has been recognised as one of the most prominent carriers and green energy source with challenging storage, enabling decarbonization. Photocatalytic H₂ (green hydrogen) production processes are targeting the intensification of separated solar energy harvesting, storage and electrolysis, conventionally yielding O₂/H₂. While catalysis is being investigated extensively, little is done on bridging the gap, related to reactor unit design, optimisation and scaling, be it that of material or of operation. Herein, metals, oxides, perovskites, nitrides, carbides, sulphides, phosphides, 2D structures and heterojunctions are compared in terms of parameters, allowing for efficiency, thermodynamics or kinetics structure–activity relationships, such as the solar-to-hydrogen (STH). Moreover, prominent pilot systems are presented summarily.     

Highly durable,Pt free and large-area Ni–B film synthesized by SILAR as a bifunctional electrode for electrochemical water splitting

A search for efficient, durable, large-area, and economic catalyst material for low-cost production of hydrogen and oxygen is currently a high priority in the field of electrocatalysis (EC). In view of this, a cost-effective, earth abundant, highly stable, Pt free, and large-area (8 cm × 8 cm) bifunctional Ni–B electrocatalyst is reported via simple and economic SILAR method. A highly porous surface of Ni–B film with high surface wettability indicated better electrochemical water-splitting properties for the films and is obtained at 100 cycles. A Low over-potential value to obtain HER (49 mV) and OER (340 mV) at 10 mA/cm² current suggested that they are comparable to the well-known Pt and RuO electrodes in alkaline medium (1M KOH), respectively. In actual water-splitting setup having Ni–B film (as cathode) and stainless steel (as anode), the hydrogen production of 612 ml/h is obtained at constant potential, which was enhanced by 18% i.e., 726 ml/h when a Ni–B film as both cathode and anode electrode was used. Both the electrodes are highly stable for over 15 days and interestingly they showed 7% increment in the EC performance.     

On the performance of improved quadrature spatial modulation

Quadrature spatial modulation (QSM) utilizes the in‐phase and quadrature spatial dimensions to transmit the real and imaginary parts of a single signal symbol, respectively. The improved QSM (IQSM) transmits two signal symbols per channel use through a combination of two antennas for each of the real and imaginary parts. The main contributions of this study can be summarized as follows. First, we derive an upper bound for the error performance of the IQSM. We then design constellation sets that minimize the error performance of the IQSM for several system configurations. Second, we propose a double QSM (DQSM) that transmits the real and imaginary parts of two signal symbols through any available transmit antennas. Finally, we propose a parallel IQSM (PIQSM) that splits the antenna set into equal subsets and performs IQSM within each subset using the same two signal symbols. Simulation results demonstrate that the proposed constellations significantly outperform conventional constellations. Additionally, DQSM and PIQSM provide a performance similar to that of IQSM while requiring a smaller number of transmit antennas and outperform IQSM with the same number of transmit antennas.