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.     

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.     

Gyrotactic microorganisms bioconvection in combined convective magnetohydrodynamic Casson nanofluid flow over a vertically surfaced saturated porous media with variable viscosity

The current article focuses on mass and thermal transfer analysis of a two-dimensional immovable combined convective nanofluid flow including motile microorganisms with temperature-dependent viscosity on top of a vertical plate through a porous medium, and a model has been developed to visualize the velocity slip impacts on a nonlinear partial symbiotic flow. The governed equations include all of the above physical conditions, and suitable nondimensional transfigurations are utilized to transfer the governed conservative equations to a nonlinear system of differential equations and obtain numerical solutions by using the Shooting method. Numerical studies have been focusing on the effects of intricate dimensionless parameters, namely, the Casson fluid parameter, Brownian motion parameter, thermophoresis parameter, Peclet number, bioconvection parameter, and Rayleigh number, which have all been studied on various profiles such as momentum, thermal, concentration, and density of microorganisms. The concentration boundary layer thickness and density of microorganisms increased as the Casson fluid parameter, Brownian and thermophoresis parameters increased, whereas the bioconvection parameter, Peclet number, and Rayleigh number increased. The thermal boundary layer thickness, concentration boundary layer thickness, and density of microorganisms all decreased. The velocity distribution decreases as the Peclet number, bioconvection, and thermophoresis parameters rise but rises as the Rayleigh number, Brownian motion parameter, and Casson fluid parameter rise. These are graphed via plots along with divergent fluid parameters.     

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.     

基于ERNIE-BiGRU模型的摘要语步自动识别研究

学术文献的摘要是对文献主要内容的浓缩,摘要不同部分的语步具有不同的信息,语步的自动识别和抽取对于学术摘要的后续研究有着重要的应用价值,而目前语步识别的研究相对较少,并且相关算法的效果还需要提高。针对上述问题,该文提出了一种基于ERNIE-BiGRU模型的语步识别算法。该算法首先结合中文句法分析理论提出基于句法依存关系的多语步结构拆分法,对学术文献摘要多语步结构进行自动拆分,获得多个单语步结构;然后构建用于训练的单语步结构语料库,并利用知识增强语义表示预训练模型,训练出句子级词向量;最后将训练出的单语步结构词向量信息输入双向门限循环单元(BiGRU)进行摘要语步自动化识别,取得了良好的效果。实验结果表明,该算法具有较好的鲁棒性和较高的识别精度,在结构化和非结构化摘要上的识别准确率分别达到了96.57%和93.75%。     

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.     

Recent Advances in Conjugated Polymers for Visible-Light-Driven Water Splitting

With the ambition of solving the challenges of the shortage of fossil fuels and their associated environmental pollution, visible-light-driven splitting of water into hydrogen and oxygen using semiconductor photocatalysts has emerged as a promising technology to provide environmentally friendly energy vectors. Among the current library of developed photocatalysts, organic conjugated polymers present unique advantages of sufficient light-absorption efficiency, excellent stability, tunable electronic properties, and economic applicability. As a class of rising photocatalysts, organic conjugated polymers offer high flexibility in tuning the framework of the backbone and porosity to fulfill the requirements for photocatalytic applications. In the past decade, significant progress has been made in visible-light-driven water splitting employing organic conjugated polymers. The recent development of the structural design principles of organic conjugated polymers (including linear, crosslinked, and supramolecular self-assembled polymers) toward efficient photocatalytic hydrogen evolution, oxygen evolution, and overall water splitting is described, thus providing a comprehensive reference for the field. Finally, current challenges and perspectives are also discussed.