Recent advances in electrocatalysts for seawater splitting in hydrogen evolution reaction

Electrocatalytic water splitting is an important method to produce green and renewable hydrogen (H₂). One of the hindrances for wide applications of electrocatalysis in H₂ production is the lack of freshwater resources. Comparatively, seawater splitting has become an effective approach for large-scale H₂ production due to its abundant reserves. However, the increased complexity of seawater content emerged more problems in electrocatalytic seawater splitting. Recently, various strategies have been reported on improving the performance of electrocatalysts applied in seawater. Herein, this review firstly analyzed the mechanisms and challenges of electrocatalytic seawater splitting to evolve H₂, and summarized the recent progress on H₂ production in electrocatalytic seawater splitting. Furthermore, suggestions for future work have been provided for guidance.     

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.     

Investigation of liquid water heterogeneities in large area proton exchange membrane fuel cells using a Darcy two-phase flow model in a multiphysics code

Proper management of the liquid water and heat produced in proton exchange membrane (PEM) fuel cells remains crucial to increase both its performance and durability. In this study, a two-phase flow and multicomponent model, called two-fluid model, is developed in the commercial COMSOL Multiphysics® software to investigate the liquid water heterogeneities in large area PEM fuel cells, considering the real flow fields in the bipolar plate. A macroscopic pseudo-3D multi-layers approach has been chosen and generalized Darcy's relation is used both in the membrane-electrode assembly (MEA) and in the channel. The model considers two-phase flow and gas convection and diffusion coupled with electrochemistry and water transport through the membrane. The numerical results are compared to one-fluid model results and liquid water measurements obtained by neutron imaging for several operating conditions. Finally, according to the good agreement between the two-fluid and experimentation results, the numerical water distribution is examined in each component of the cell, exhibiting very heterogeneous water thickness over the cell surface.     

Pristine and cobalt doped copper sulfide microsphere particles for seawater splitting

In this work, copper sulfide particles are synthesized with different Co doping concentrations such as 0, 1 and 5% at 80 °C by optimizing synthesis times from 1 to 3 h. Copper sulfide particles possess two structural phases of covellite CuS and digenite Cu₉S₅. The increase in synthesis time from 1 to 3 h increases the Cu₉S₅ phase growth and changes the morphology from flower to microsphere. The CuS synthesized with 0, 1 and 5% Co dopant concentrations demonstrate flower consisting of agglomerated nanosheets, microsphere and flower like microsphere. The elemental investigation substantiates Co ions presence in CuS microspheres. The A_1g (LO) mode intensity is decreased with increase in Co dopant concentration confirming Co incorporation into CuS microsphere. The CuS synthesized with 0, 1, 5% Co dopants exhibit 322 mV, 305 mV and 289 mV to attain 100 mA/cm² in 1 M KOH seawater. The CuS synthesized with 5% Co dopant demonstrates higher double layer capacitance (C_dl) of 173.9 mFcm^?2 and lower charge transfer resistance (R_ct) of 6.07 Ω with 78.84% retention after 10 h continuous stability than that of the other pristine (118.3 mFcm^?2, 13.72 Ω) and 1% Co doped CuS microsphere (165.7 mFcm^?2, 8.55 Ω) indicating more surface active site and rapid charge carrier transport, respectively.     

The dynamic effect of Micro-MHD convection on bubble grown at a horizontal microelectrode

Relatively low efficiency is the biggest obstacle to the popularization of water electrolysis, which is a particularly feasible way to produce super-pure hydrogen. Imposing a magnetic field can increase the hydrogen production efficiency of water electrolysis. However, the enhancement's detailed mechanism still lacks an insightful understanding of the bubbles' micro vicinity. Our recent work aims to understand why the micro-magnetohydrodynamic (MHD) convection hinders single bubbles' detachment on the microelectrode. A water electrolysis experiment by microelectrode is performed under an electrode-normal magnetic field, and dynamic analysis of the single bubble growing on microelectrodes is performed. The variation of bubble diameter with time in the presence or absence of the magnetic field was measured, and the forces acting on the bubble were quantified. The result shows that the micro-MHD convection, induced by Lorentz force, can give rise to a downward hydrodynamic pressure force that will not appear in large-scale MHD convection. This force can be of the same magnitude as the surface tension, so it dramatically hinders bubbles' detachment. Besides, the Kelvin force provides a new potential way for further improving the efficiency of water electrolysis.     

Dysprosium doped copper oxide (Cu1-xDyxO) nanoparticles enabled bifunctional electrode for overall water splitting

The production of hydrogen, a favourable alternative to an unsustainable fossil fuel remains as a significant hurdle with the pertaining challenge in the design of proficient, highly productive and sustainable electrocatalyst for both oxygen evolution reaction (OER) and hydrogen evolution reaction (HER). Herein, the dysprosium (Dy) doped copper oxide (Cu_1-xDy_xO) nanoparticles were synthesized via solution combustion technique and utilized as a non-noble metal based bi-functional electrocatalyst for overall water splitting. Due to the improved surface to volume ratio and conductivity, the optimized Cu_1-xDy_xO (x = 0.01, 0.02) electrocatalysts exhibited impressive HER and OER performance respectively in 1 M KOH delivering a current density of 10 mAcm^?2 at a potential of ?0.18 V vs RHE for HER and 1.53 V vs RHE for OER. Moreover, the Dy doped CuO electrocatalyst used as a bi-functional catalyst for overall water splitting achieved a potential of 1.56 V at a current density 10 mAcm^?2 and relatively high current density of 66 mAcm^?2 at a peak potential of 2 V. A long term stability of 24 h was achieved for a cell voltage of 2.2 V at a constant current density of 30 mAcm^?2 with only 10% of the initial current loss. This showcases the accumulative opportunity of dysprosium as a dopant in CuO nanoparticles for fabricating a highly effective and low-cost bi-functional electrocatalyst for overall water splitting.     

Synthesis of bristlegrass-like Co-doped Ni2P composites on Ni foam for overall seawater splitting

Seawater is the most abundant resource on earth, so developing cost-effective, highly durable corrosion resistance and efficient electrocatalysts are crucial to enhance seawater splitting. Herein, we prepared 3D bristlegrass-like Co-doped Ni₂P (Co-Ni₂P) composites supported on Ni foam (NF) through a facile solvothermal method combined and a subsequent phosphatization treatment. Benefiting from the unique structure, Co-Ni₂P shows excellent electrocatalytic activity as an electrode material for both the hydrogen evolution reaction (HER, low overpotential of 116 mV at 50 mA cm^?2) and oxygen evolution reaction (OER, low overpotential of 266 mV at 50 mA cm^?2). Moreover, the as-prepared Co-Ni₂P composites exhibit excellent stability and corrosion resistance in an alkaline medium. Density functional theory (DFT) calculations were employed to evaluate the H1 adsorption of Co-Ni₂P, and the results proved the high catalytic activity for the HER. This study provides new materials with a unique morphology for overall water splitting.     

Designing independent water transport channels to improve water flooding in ultra-thin nanoporous film cathodes for PEMFCs

Utilization of 3D nanostructured Pt cathodes could obviously improve performances of proton exchange membrane fuel cells (PEMFCs) owing to the reduced tortuosity and the bi-continuous nanoporous structure. However, these cathodes usually suffer from the flooding problem ascribed to the ionomer-free and nanoscale pores which are more susceptible to water condensation. In this paper, ultra-thin nanoporous metal films (100 nm) were utilized to construct PEMFC cathodes and independent transport channels were designed separately for water and gas aiming at the flooding problem. Nanoporous gold (NPG) film was used as the model support for loading Pt nanoparticles owing to its controllable and stable structure. After optimizing the polytetrafluoroethylene (PTFE) content and carbon loading in the gas diffusion layer (GDL), plasma treatment under O₂ atmosphere was used to pattern the GDL with independent water transport channels. The obtained liquid permeation coefficients and oxygen gains demonstrated the obviously improved water and O₂ transport. By using a home-made optimized GDL and a nanoporous film cathode with pore size ～60 nm, the flooding problem could be facilely solved. With a Pt loading of ～16 μg cm^?2, this 3D nanostructured cathode exhibits a PEMFC performance of ～957 mW cm^?2 at 80 °C. The Pt power efficiency is about 4 times higher than that of the commercial Pt/C cathode (50 μg cm^?2, 756 mW cm^?2). Obviously, this study provides a simple but effective methodology to solve the water flooding problem in the ultra-thin nanoporous film cathodes which is applicable for other types of 3D nanostructured PEMFC cathodes.     

Electronic regulation and core-shell hybrids engineering of palm-leaf-like NiFe/Co(PO3)2 bifunctional electrocatalyst for efficient overall water splitting

Constructing efficient and stable bifunctional electrocatalysts for overall water splitting remains a challenge because of the sluggish reaction kinetics. Herein, the core-shell hybrids composed of Co(PO₃)₂ nanorod core and NiFe alloy shell in situ grown on nickel foam (NiFe/Co(PO₃)₂@NF) are synthesized. Owing to the hierarchical palm-leaf-like structures and strong adhesion between NiFe alloys, Co(PO₃)₂ and substrates, the catalyst provides a large surface area and rapid charge transfer, which facilitates active sites exposure and conductivity enhancement. The interfacial effect in the NiFe/Co(PO₃)₂ core-shell structure modulates the electronic structure of the active sites around the boundary, thereby boosting the intrinsic activity. Benefiting from the stable structure, the durability of the catalyst is not impaired by the inevitable surface reconfiguration. The NiFe/Co(PO₃)₂@NF electrode presents a low cell voltage of 1.63 V to achieve 10 mA cm^?2 and manifests durability for up to 36 h at different current densities.     

Numerical study of entropy generation in Darcy-Forchheimer (D-F) Bödewadt flow of CNTs

Three-dimensional Bödewadt flow (fluid rotates at a large enough distance from the stationary plate) of carbon nanomaterial is examined. Single walled and multi walled CNTs are dissolved in water and gasoline oil baseliquids. Darcy-Forchheimer porous medium is considered. Stationary disk is further stretched linearly in radial direction. Heat transfer effect is examined in presence of radiation and convection. Effect of viscous dissipation is accounted. Entropy generation rate is studied. By using adequate transformation (von Kármán relations), the flow field equations (PDEs) are transmitted into ODEs. Solutions to these ODEs are constructed via implementation of shooting method (bvp4c). In addition to Entropy generation rate, Bejan number, heat transfer rate (Nusselt number), skin friction and temperature of fluid are examined through involved physical parameters. Axial component of velocity intensifies with increment in nanoparticles volume fraction and ratio of stretching rate to angular velocity parameter while it decays with higher porosity parameter. Higher nanoparticles volume fraction and porosity parameter lead to decay in radial as well as tangential component of velocity. However it enhances with higher ratio of stretching rate to angular velocity parameter. Temperature of fluid directly varies with higher ratio of stretching rate to angular velocity parameter, radiation parameter, Eckert number, Biot number and nanoparticles volume fraction. Rate of Entropy generation is reduced with higher estimations of porosity parameter, nanoparticles volume fraction and radiation parameter. Skin friction coefficient decays with higher porosity parameter and ratio of stretching rate to angular velocity parameter. Intensification in porosity parameter, nanoparticles volume fraction and Biot number leads to higher Nusselt number. Prominent impact is shown by multiple-walled CNTs with gasoline oil basefluid than single-walled CNTs with water basefluid.