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.     

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.     

Precipitous weakening of quartz at the α–β phase inversion

Crystalline quartz has long been identified as among the weakest of abundant crustal minerals. This weakness is particularly evident around the α–β phase inversion at 573°C, in which Si–O bonds undergo a displacive structural transformation from trigonal to hexagonal symmetry. Here we present data using indentation testing methodologies that highlight the precipitous extent of the transformational weakening. Although the indentations are localized over relatively small specimen contact areas, the data quantify the essential deformation and fracture properties of quartz in a predominantly (but not exclusively) compressive stress field, at temperatures and pressures pertinent to conditions in the earth's crust.     

Dense and core-rim structured B4C-TiB2 ceramics with Mo-Co-WC additive

B₄C-TiB₂ ceramics (TiB₂ ranging 5~70 vol%) with Mo-Co-WC as the sintering additive were prepared by spark plasma sintering. In comparison with B₄C-TiB₂ without additive, the enhanced densification was evident in the sintered specimen with Mo-Co-WC additive. Core-rim structured grain was observed around TiB₂ grains. The interface of the rim between TiB₂ and B₄C phases demonstrated different feature: the inner borderline of the rim exhibited a smooth feature, whereas a sharp curved grain boundary was observed between the rim and the B₄C grain. The formation mechanism is discussed: the epitaxial growth of (Ti,Mo,W)B₂ rim around the TiB₂ core may occur as a result of the solid solution and dissolution-precipitation between TiB₂ phase and the sintering additive. It was revealed that the fracture toughness increased as the content of TiB₂ content increased, alongside the decreased hardness. B₄C-30 vol% TiB₂ specimen demonstrated the optimal combination of mechanical properties, reaching Vickers hardness of 24.3 GPa and fracture toughness of 3.33 MPa·m^1/2.     

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.     

Pressure-induced transparency of MgO,Al2O3, AlN,and cBN ceramics at room temperature

The in situ axial X-ray diffraction patterns of four ceramic powder samples (MgO, Al₂O₃, AlN, and cBN) that were compressed in a diamond anvil cell under uniaxial non-hydrostatic conditions were recorded. The microscopic deviatoric stress as a function of the pressure was determined from the X-ray diffraction peak broadening analysis: the curves increased approximately linearly with the pressure at the initial compression stage and then levelled off under further compression. Pressure-induced transparency was observed in all of the samples under compression, and the pressure at the turning point on the curves of the microscopic deviatoric stress versus pressure corresponded to the pressure at which the samples became transparent. Analysis of the microstructural features of the pressure-induced transparent samples indicated that the compression caused the grains to fracture, and the broken grains bonded with each other. We demonstrated that the ceramics’ pressure-induced transparency was a process during which the grains were squeezed and broken, the pores were close between the grains, and the broken grains were re-bonded under compression.     

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.     

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.     

Mesoporous g-C3N4 decorated by Ni2P nanoparticles and CdS nanorods together for enhancing photocatalytic hydrogen evolution

Ni₂P nanoparticles and CdS nanorods were grew together on a mesoporous g-C₃N₄ through a facile in-situ solvothermal approach. Under visible light (λ > 400 nm), the as-prepared ternary PCN–CdS-5% Ni₂P composite displays a high H₂ evolution rate with 2905.86 μmol g^?1 h^?1, which is about 14, 18 and 279 times that of PCN–CdS, PCN–Ni₂P and PCN, respectively. The enhanced photocatalytic activity is mainly attributed to the improved separation efficiency of the photocarriers by the type II PCN–CdS heterojunction and the effective extraction of photogenerated electrons by Ni₂P. Meanwhile, Ni₂P acts as co-catalyst to provide the photocatalytic active site for hydrogen reduction. In addition, PCN–CdS-5% Ni₂P composite exerts good stability in 12-h cycles.