Commercial Hydrogen Production Research Articles

Three-dimensional NiCo2O4 nanosheets and nanoflowers electrodeposited with palladium nanoparticles on nickel foam for the hydrogen evolution reaction

By combining NiCo2O4 with good hydrogen evolution reaction (HER) properties and palladium (Pd) nanoparticles with excellent conductivity, a highly efficient and stable catalyst is prepared for HER. The NiCo2O4 nanosheets and NiCo2O4 nanoflowers are produced on the nickel foam (NF) with a large specific surface area by a one-step hydrothermal method and the NiCo2O4 nanoflowers are uniformly distributed in the NiCo2O4 nanosheets to form a three-dimensional (3D) electrode. Compared to conventional NiCo2O4, the 3D NiCo2O4 electrode provides more active sites (Ni and Co) for oxygen adsorption thus reducing the energy required to break H–O bonds to promote HER. When NiCo2O4/NF is combined with Pd nanoparticles (Pd/NiCo2O4/NF), the HER performance is improved greatly because of the synergistic effects rendered by the 3D structure of NiCo2O4 and Pd nanoparticles. The overpotential of Pd/NiCo2O4/NF is 69 mV at a current density is 10 mA/cm2 and it is stable for 10 h in alkaline environments. The materials design and properties provide useful information for future development of commercial hydrogen production.

Conductivity Modulation of 3D‐Printed Shellular Electrodes through Embedding Nanocrystalline Intermetallics into Amorphous Matrix for Ultrahigh‐Current Oxygen Evolution

AbstractScaling up commercial hydrogen production by water electrolysis requires efficient oxygen evolution reaction (OER) electrodes that can deliver large current densities (more than 500 mA cm−2) at low overpotentials. Here, a highly active and conductive shell‐based cellular (Shellular) electrode is developed through a strategy of embedding nanocrystalline Ni3Nb intermetallics into an amorphous NiFe‐OOH matrix. The tailor‐made laser remelting process enables the dispersive precipitation of corrosion‐resistant nanocrystalline Ni3Nb in large numbers. After in situ electrochemical activation in the self‐developed growth‐mode‐control electrolyte, the amorphous NiFe‐OOH nanosheets and nanocrystalline Ni3Nb are formed on the as‐printed Inconel 718. The conductive atomic force microscopy (C‐AFM) studies and density functional theory (DFT) calculations elucidate that nanocrystalline Ni3Nb can simultaneously enhance the conductivity and activity of the catalyst film. Additionally, a Shellular structure inspired by nature is designed, interestingly, its specific surface area keeps constant with increases in porosity. This design can result in a large surface area and high porosity but with less material cost. Using this electrochemically activated Shellular electrode for OER, a high current density of 1500 mA cm−2 is achieved at a record‐low overpotential of 261 mV with good durability. This development may open the door for large‐scale industrial water electrolysis.

Nano-casting procedure for catalytic cobalt oxide bead preparation from calcium-alginate capsules: Activity in ammonia borane hydrolysis reaction

The preparation of bead type catalysts, which had a rapid and easy recoverable property for reusability and regeneration procedures during ammonia borane (NH3BH3) hydrolysis, was the main scope of this study. In the present study, the nano-casting procedure was adapted to cobalt oxide (Co3O4) microbeads preparation by multi-step ions exchange procedures. By nano-castings -, cobalt-alginate capsules provided the formation of a surface-active bead (140 ± 0.4 μm) in Co3O4 nanoparticles (25–35 nm) with enhanced performance for releasing of hydrogen from NH3BH3. Moreover, the catalysts used for 555 min without any mechanical damages during reusability tests and regeneration procedure. The bead type catalyst enabled the rapid and easy recover at the end of the reaction that improved the reuse of catalysts for the practical and curial for a commercial on-board hydrogen production application.

Membrane Electrode Assemblies Fabricated By Reactive Spray Deposition Technology for Advanced Proton Exchange Membrane Water Electrolyzers: Study of the Degradation Mechanisms

Proton exchange membrane water electrolyzers (PEMWEs) have demonstrated great potential as the next generation hydrogen production technology1,2. The main challenges that the state-of-the-art PEMWEs are currently facing are: (i) high cost, (ii) low efficiency, and (iii) poor durability performance3. Understanding the failure modes of PEMWEs during the operation is a key factor for improving their durability performance, as well as for lowering the precious metal loading in the catalyst layers and hence for reducing their cost. However, the catalyst degradation mechanisms in PEMWEs during operation, especially for the Ir-based anode catalysts, have not been fully understood.In this work, reactive spray deposition technology (RSDT) has been used to fabricate membrane electrode assemblies (MEAs) with one order of magnitude lower Pt and Ir catalyst loadings in their cathode and anode catalyst layers, respectively, in comparison to the precious metals loading in the state-of-the-art commercial MEAs for PEMWEs 4–6. Two of as- fabricated MEAs with geometric area of 86 cm2, have been tested at steady-state conditions that are typical for commercial hydrogen production system. One of the cells was stopped and disassembled after 50 hours of operation, while the second one was disassembled after it failed after over 500 hours of operation. Herein we present a comprehensive comparative study of both MEAs, aimed at identifying and understanding the degradation mechanisms causing the MEAs failure. The pre- and post-test MEA characterizations are performed by scanning/transmission electron microscopy (S/TEM), scanning electron microscopy (SEM), inductively coupled plasma optical emission spectroscopy (ICP-OES), X-ray diffraction (XRD) and X-ray computed tomography (X-CT). In addition, rotating disk electrode (RDE) technique has been utilized for assessment of the catalytic activities of the RSDT-fabricated anode Ir/IrOx catalysts before and after the failure. The main degradation mechanisms, governing the failure modes in the MEAs of interest, have been identified and discussed. References Carmo, M., Fritz, D. L., Mergel, J. & Stolten, D. A comprehensive review on PEM water electrolysis. Int. J. Hydrogen Energy 38, 4901–4934 (2013).Babic, U. et al. Critical Review — Identifying Critical Gaps for Polymer Electrolyte Water Electrolysis Development Review — Identifying Critical Gaps for Polymer Electrolyte Water. (2017). doi:10.1149/2.1441704jesButtler, A. & Spliethoff, H. Current status of water electrolysis for energy storage, grid balancing and sector coupling via power-to-gas and power-to-liquids: A review. Renew. Sustain. Energy Rev. 82, 2440–2454 (2018).Roller, J. M. & Maric, R. A Study on Reactive Spray Deposition Technology Processing Parameters in the Context of Pt Nanoparticle Formation. J. Therm. Spray Technol. 24, 1529–1541 (2015).Roller, J. M., Kim, S., Kwak, T., Yu, H. & Maric, R. A study on the effect of selected process parameters in a jet diffusion flame for Pt nanoparticle formation. J. Mater. Sci. 52, 9391–9409 (2017).Yu, H. et al. Nano-size IrOx catalyst of high activity and stability in PEM water electrolyzer with ultra-low iridium loading. Appl. Catal. B Environ. 239, 133–146 (2018).

NiFe-Layered Double Hydroxide Synchronously Activated by Heterojunctions and Vacancies for the Oxygen Evolution Reaction.

The development of earth-abundant transition-metal-based electrocatalysts with bifunctional properties (oxygen evolution reaction (OER) and hydrogen evolution reaction (HER)) is crucial to commercial hydrogen production. In this work, layered double hydroxide (LDH)-zinc oxide (ZnO) heterostructures and oxygen vacancies are constructed synchronously by plasma magnetron sputtering of NiFe-LDH. Using the optimal conditions, ZnO nanoparticles are uniformly distributed on the NiFe-LDH nanoflowers, which are prepared uniformly on the three-dimensional porous Ni foam. In the LDH-ZnO heterostructures and oxygen vacancies, electrons are depleted at the Ni cations on the NiFe-LDH surface and the active sites change from Fe cations to Ni cations during OER. Our theoretical assessment confirms the change of active sites after the deposition of ZnO and reveals the charge-transfer mechanism. Owing to the significant improvement in the OER dynamics, overall water splitting can be achieved at only 1.603 V in 1 M KOH when the Ni/LDH-ZnO and Ni/LDH are used as the anode and cathode, respectively. The work reveals a novel design of self-supported catalytic electrodes for efficient water splitting and also provides insights into the surface modification of catalytic materials.

Clean Fuel from Nuclear Power

Abstract The current commercial hydrogen production has a significant carbon footprint. Now, projects co-funded by the U.S. Department of Energy and commercial nuclear utilities with operating nuclear power facilities aim to change that by exploiting the capabilities of nuclear power plants. This article delves into four projects aimed at demonstrating technology to make hydrogen from water on an industrial scale using energy from an operating commercial nuclear power plant.

An Fe-doped Co11(HPO3)8(OH)6 nanosheets array for high-performance water electrolysis

The water electrolysis for commercial hydrogen production is dependent on efficient and economical electrocatalysts toward both half reactions of oxygen evolution reaction (OER) and hydrogen evolution reaction (HER). In this work, an Fe-doped Co11(HPO3)8(OH)6 nanosheets array was fabricated on Ni foam via a one-step liquid-phase approach in the solvents of deionized water and isopropyl alcohol as such a bifunctional electrocatalyst. The different proton acceptors of hydroxyl and phosphite in Co11(HPO3)8(OH)6 nanosheets expedited the proton and electron transfer. The Fe dopant in Co11(HPO3)8(OH)6 adjusted the electronic structure of Co11(HPO3)8(OH)6, which significantly increased the hydrophilicity, conductivity, and active surface area. The density functional theory (DFT) calculations showed the Gibbs free energy of OER intermediates and H* adsorption energy in HER process were lowered, while the density of states (DOS) in the d-band center was increased by Fe doping, suggesting that Fe-doped Co11(HPO3)8(OH)6 is more active towards OER and HER processes. As a result, the optimized Fe11.7%-Co11(HPO3)8(OH)6 shows outstanding activity, durability and robust structural stability toward both OER and HER in 1 M KOH electrolyte. For OER, it outputs 20 mA cm−2 merely at an overpotential of 206 mV. Benefited from monolithically integrated nanosheets array structure on Ni foam, it can stably drive 500 mA cm−2 at a fairly low overpotential of 268 mV. For HER, low overpotentials of 102 mV for 10 mA cm−2 and 263 mV for 500 mA cm−2 are acquired on Fe11.7%-Co11(HPO3)8(OH)6. This offers a water-alkali electrolyzer by two Fe11.7%-Co11(HPO3)8(OH)6 electrodes implements a low cell voltage of 1.494 V for 10 mA cm−2, and 1.772 V for 500 mA cm−2 toward overall water electrolysis with striking stability. This work opens a promising avenue in exploring highly active and stable catalysts by transition metal phosphites with suitable element doping toward scale-up water electrolysis.

Interfacial Engineering FeOOH/CoO Nanoneedle Array for Efficient Overall Water Splitting Driven by Solar Energy.

Interface engineering has been applied as an effective strategy to boost the electrocatalytic performance because of the strong coupling and synergistic effects between individual components. Here, we engineered vertically aligned FeOOH/CoO nanoneedle array with a synergistic interface between FeOOH and CoO on Ni foam (NF) by a simple impregnation method. The synthesized FeOOH/CoO exhibits outstanding electrocatalytic activity and stability for both hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) in an alkaline medium. For the overall water splitting, the bifunctional FeOOH/CoO nanoneedle catalyst requires only a cell voltage of 1.58 V to achieve a current density of 10 mA cm-2 , which is much lower than that required for IrO2 //Pt/C (1.68 V). The FeOOH/CoO catalyst has been successfully applied for solar cell-driven water electrolysis, revealing its great potential for commercial hydrogen production and solar energy storage.

Effect of shunt honeycomb ceramics thickness on finned tube heat transfer in VAM oxidation for hydrogen production

Shunt honeycomb ceramics (SHC) are proposed to constrain operation parameter fluctuation within commercial hydrogen production through gasification method with the steam produced with ventilation air methane oxidation heat. However, the effect of SHC thickness on heat extraction trait was ignored in the former studies. An improved numerical simulation was carried out to study the effect of SHC thickness. Results show that the existence of SHC increases pressure drop is increased by 23.5%, decrease the temperature difference between inlet and outlet, increases average heat flux may be increased by 7.4%. Radiation heat transfer accounts for 0.2374–0.3398 of total heat exchange, and as the SHC thickness grows, radiation heat transfer increases gradually.

Oxygen-Incorporated NiMoP2 Nanowire Arrays for Enhanced Hydrogen Evolution Activity in Alkaline Solution

Catalytic water splitting for commercial hydrogen production demands efficient and robust earth-abundant catalysts. However, sluggish kinetics of water dissociation in alkaline electrolyte impedes the formation of reactive intermediates by discharge of water. Here, oxygen-incorporated NiMoP2 nanowire arrays are engineered on Ni foam substrate (denoted as O-NiMoP2/Ni) by controllable partial phosphorization of metal oxide precursors to boost HER activity under alkaline environment. The incorporation of oxygen can significantly modify the electronic structure of NiMoP2 and optimize both HER Gibbs free-energy change (ΔGH*) and water adsorption energy change (ΔGH2O*). Results demonstrate that the O-NiMoP2/Ni nanowire arrays require quite low HER overpotentials of 31 and 134 mV to drive the geometrical catalytic current densities of 10 and 100 mA cm–2, respectively. The activity and stability in 1 M KOH are also superior to those of the state-of-the-art transition-metal phosphides (TMPs).

Ternary Ni2(1-x)Mo2xP nanowire arrays toward efficient and stable hydrogen evolution electrocatalysis under large-current-density

Developing efficient nonprecious electrocatalysts for hydrogen evolution reaction (HER) in alkaline media at large-current-density is appealing and challenging for large-scale water electrolysis. Here, we present a theoretical and experimental study to demonstrate that ternary Ni2(1-x)Mo2xP porous nanowire arrays grown on Ni foam, as a highly efficient and stable electrocatalyst toward alkaline HER under large-current-density. Density functional theory (DFT) calculations reveal that Mo substitution of Ni in Ni2P leads to optimal free energy of water activation and hydrogen adsorption on the catalyst surface. Benefiting from the enhanced intrinsic activity, large active surface area and fast gas releasing, the Ni2(1-x)Mo2xP catalyst exhibits an excellent HER activity with low overpotentials of 72, 240, and 294 mV at current densities of 10, 500, and 1000 mA cm−2, respectively, along with superior stability in 1 M KOH. This highly active and stable catalyst enables an electrolyzer operating at 10 mA cm−2 at a voltage of 1.51 V, 100 mA cm−2 at 1.65 V, and 500 mA cm−2 at 1.82 V in 1 M KOH at room temperature, which are much better than the benchmark of IrO2/Pt. Our 3D ternary Ni2(1-x)Mo2xP catalysts significantly advance the science and technology for commercial hydrogen production.

Crossed FeCo2S4 nanosheet arrays grown on 3D nickel foam as high-efficient electrocatalyst for overall water splitting

Great efforts in developing low-cost, highly efficient and stable electrocatalysts are to tune the chemical compositions and morphological characteristics for enhancing efficiency of water splitting. In this communication, FeCo2S4 nanosheet was grown in situ on nickel foam (FeCo2S4/NF) via a facile hydrothermal sulfidization method and served as a high-efficient bifunctional electrocatalyst for overall water splitting. As-synthesized FeCo2S4/NF self-supported electrode delivers 20 mA cm−2 at an overpotential of 259 mV toward OER and 10 mA cm−2 at an overpotential of 131 mV toward HER in alkaline media. Moreover, when used as both anode and cathode in a two-electrode electrolyzer, only a small cell voltage of 1.541 V is needed to afford a current density of 10 mA cm−2 for overall water splitting. Bifunctional electrode FeCo2S4/NF also revealed a distinguished electrochemical durability during a 12 h stability test at 1.63 V, which would provide a promising water splitting installation for commercial hydrogen production.

Alumina-Supported CoPS Nanostructures Derived from LDH as Highly Active Bifunctional Catalysts for Overall Water Splitting

It is highly desirable to develop efficient and low-cost electrocatalysts to boost the water-splitting reaction, which has been regarded as one of the ideal methods for commercial hydrogen production. Herein, the ultrathin amorphous Al2O3 nanosheets decorated with CoPS nanoparticles (size: 4–12 nm) were successfully synthesized using a CoAl-layered double hydroxide (CoAl-LDH) as precursor. The as-prepared catalysts exhibit low onset overpotential of 67 mV for the hydrogen evolution reaction and 250 mV for the oxygen evolution reaction together with good stability in an alkaline medium. Moreover, employed as the bifunctional electrocatalysts with a two-electrode electrolyzer, the CoPS nanostructure also produced a small cell voltage of 1.75 V to attain 10 mA cm–2. The excellent electrocatalytic performance could be attributed not only to the high electron-donating and electron-accepting characters of P2– ligands and Co3+ ions, respectively, but also to the large active surface area and porous structure of ...

Performance evaluation of hydrogen production based on off-peak electric energy of the nuclear power plant

The article investigates the efficiency of commercial hydrogen production by water electrolysis on the base of NPP excess energy with its additional purification higher than 99.9999%, considering its transport. The competitive high purity hydrogen release price has been determined as compared to the market price. Besides, the use of high duty electrolysis plants has been suggested. Moreover, the advantages of water electrolysis cyclic operation while consuming electric energy from NPP as compared to the continuous mode have been presented in the paper.

Highly active catalyst derived from a 3D foam of Fe(PO3)2/Ni2P for extremely efficient water oxidation

Commercial hydrogen production by electrocatalytic water splitting will benefit from the realization of more efficient and less expensive catalysts compared with noble metal catalysts, especially for the oxygen evolution reaction, which requires a current density of 500 mA/cm2 at an overpotential below 300 mV with long-term stability. Here we report a robust oxygen-evolving electrocatalyst consisting of ferrous metaphosphate on self-supported conductive nickel foam that is commercially available in large scale. We find that this catalyst, which may be associated with the in situ generated nickel-iron oxide/hydroxide and iron oxyhydroxide catalysts at the surface, yields current densities of 10 mA/cm2 at an overpotential of 177 mV, 500 mA/cm2 at only 265 mV, and 1,705 mA/cm2 at 300 mV, with high durability in alkaline electrolyte of 1 M KOH even after 10,000 cycles, representing activity enhancement by a factor of 49 in boosting water oxidation at 300 mV relative to the state-of-the-art IrO2 catalyst.

Experimental studies and modeling of advanced alkaline water electrolyser with porous nickel electrodes for hydrogen production

The commercial hydrogen production by water electrolysis is limited by the high cost of electricity. The production cost can be minimized, if the cell module is operated with the minimum voltage at maximum current density. In the present study, porous nickel electrodes were developed indigenously on an engineering scale and used in an advanced zero gap filter press type bipolar electrolyser to minimize the cell voltage. As the cell voltage–current density characteristic of the cell module is unique feature of its design and the operating parameters, the polarization experiments were carried out using this cell module and the cell voltage–current density characteristics were generated at different operating temperatures. Further, the system is modelled for its electrochemical performance and the parameters accounting for different losses such as Ohmic and activation over potential, were estimated at different temperatures. These different parameters were compared with the data existing in literature and based on the analysis, the present cell module is found to be superior to the existing commercial electrolyzers in terms of energy efficiency.

알칼라인 수전해용 Ni-Fe 합금 전착 전극의 특성

Alkaline water electrolysis is commercial hydrogen production technology. It is possible to operate MW scale plant. Because It used non-precious metal for electrode. But It has relatively low current density and low efficiency. In this study, research objective is development of anode for alkaline water electrolysis with low cost, high corrosion resistance and high efficiency. Stainless steel 316L (SUS 316L) was selected for a substrate of electrode. To improve corrosion resistance of substrate, Nickel (Ni) layer was electrodeposited on SUS 316L. Ni-Fe alloy was electrodeposited on the passivated Ni layer as active catalyst for oxygen evolution reaction(OER). We optimized preparation condition of Ni-Fe alloy electrodeposition by changing current density, electrodeposition time and composition ratio of Ni-Fe electrodeposition bath. This electrodes were electrochemically evaluated by using Linear sweep voltammetry (LSV) and Cyclic voltammetry (CV). The Ni-Fe alloy (Ni : Fe = 1 : 1) showed best activity of OER. The optimized electrode decreased overpotential about 40% at <TEX>$100mA/cm^2$</TEX> compared with Ni anode.

PERFORMANCE EVALUATION OF HYDROGEN PRODUCTION ON BASE OF THE OFF-PEAK ELECTRICITY OF ATOMIC POWER STATION

The article investigates efficiency of commercial hydrogen production by electrolysis of water on base of the surplus electricity of atomic power station with additional purification of his in membrane plant higher than 99.9999 percent and also with calculation cost of transportation. It is determined competitive sale price of hydrogen with high degree of purification by compare with market price. It is proposed to use the high power electrolysis plants. More - over, the article shows advantage of cyclical regime electrolysis of water at consumption of electricity from atomic power station in compare with stationary regime.

초고온가스로를 이용한 원자력수소생산 기술개발

미래에너지의 해법으로 원자력에너지를 이용한 물분해 수소생산시스템의 핵심기술을 개발하였다. 안전성을 보장할 수 있는 제4세대 원자로인 초고온가스로의 고열을 이용하여 황요오드 열화학적인 방법으로 물을 분해하여 수소를 생산하는 기술이다. 원자력수소생산 핵심기술은 초고온에서의 열을 공급하는 것을 모사하는 초고온 실험기술, 초고온가스로의 안전성을 모사하는 연구, 초고온가스로의 노심과 안전성을 해석할 수 있는 도구의 개발, 초고온가스로에 사용하는 연료제조기술, 물을 분해하여 열화학적인 방법으로 수소를 생산하는 기술로 구성된다. 원자력수소생산에 필요한 핵심기술을 개발하고 실험실 규모로 입증하였으며, 대규모 실용화를 위해서 선결되어할 미완성 기술을 제시하였다. 본 기술은 제4세대 원자로개발 국제공동연구로 수행한 기술로서 향후 미래의 원자로 기술이다.

Control of oxygen delamination in solid oxide electrolyzer cells via modifying operational regime

Modifications of operational regimes for solid oxide electrolyzer cell (SOEC) devices for hydrogen production are discussed. It is shown that applying alternating current voltage pulses at a certain frequency range to SOECs could reduce oxygen delamination degradation in these devices and significantly increase their lifetime. This operational scheme provides possibility to increase longevity of SOEC devices required for their use in commercial hydrogen production processes, without any significant modification of used materials and/or cell design.