Hierarchical Co/MoO2@N-doped carbon nanosheets derived from waste lotus leaves for electrocatalytic water splitting

It is imperative for electrochemical water splitting to seek functional materials with high performance, competence, durability, economical, and eco-friendly. Herein, we develop a simplistic two-step annealing strategy to synthesize the hierarchical Co/MoO₂@nitrogen (N)-doped carbon nanosheets (CMO@NC) electrocatalysts derived from the low-cost and sustainable lotus leaves biomass for water-splitting. The optimum catalyst (CMO@NC/450) exhibits a notable low overpotential of 130 and 272 mV at a current density of 10 mA cm^?2 for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) in 1.0 M KOH, owing to their unique surface features, large surface area, abundant meso/micropores, and high pyridinic N-contents. Also, the CMO@NC/450 catalyst-equipped with a two-electrode configuration exhibits notable water splitting activity only requires a cell-potential of 1.629 V@10 mA cm^?2 in 1.0 M KOH. The results reveal that hierarchical flower-like morphology increases the contact area, prevents aggregation, and enables massive active-sites for HER and OER. Additionally, the synergistic effects between Co/MoO₂ and the N-doped-carbon heterostructure enhance charge-delocalization, ultimately improving electrocatalytic performance and stability. This work is aimed to promote the exploration and design of suitable doping structures and compositions for the development of highly effective and sustainable biomass-derived catalysts in a wide-range of electrochemical applications.     

Efficient CoMoRu0.25Ox/NF nanoplate architectures for overall electrochemical water splitting

The development of inexpensive electrocatalysts with excellent electrocatalytic activity for the hydrogen and oxygen evolution reactions (HER and OER, respectively) has been challenging. In this study, we synthesized cobalt molybdenum ruthenium oxide with porous, loosely-assembled nanoplate morphology. The CoMoRu_0.25O_x/NF electrocatalyst exhibited the highest electrocatalytic activity, requiring overpotentials of 230 and 78 mV for the OER and HER, respectively, to attain a current density of 10 mA cm^?2; moreover, its long-term stability was outstanding. The electrocatalyst required a cell voltage of only 1.51 V for overall water splitting in an alkaline medium, which was lower than that required by many CoMo-based catalysts.     

CoP-anchored high N-doped carbon@graphene sheet as bifunctional electrocatalyst for efficient overall water splitting

Electrocatalytic water splitting, as an ideal technology in renewable energy applications, suffers from high electrical energy consumption due to the slow kinetics of HER and OER reactions. Therefore, it is urgent to design efficient bifunctional catalysts to improve the reaction kinetics. Herein, a self-supported electrode, anchoring CoP nanoparticles on N-doped carbon/graphene (NC-G) and chemically growing on Ni foam as a whole electrode (denoted as NC-G-CoP/NF) displays promising electrocatalytic performance in 1.0 M KOH electrolyte, with a low overpotentials of 68 mV at 10 mA cm^?2 for HER and 255 mV at 50 mA cm^?2 for OER. This bifunctional electrocatalyst only needs 1.435 V to generate 10 mA cm^?2 for overall water splitting. The outstanding electrocatalytic performance is ascribed to the following factors: i) inherent nature of transition metal phosphides, ii) abundant and high dispersion N active sites in NC-G, iii) strong interaction between the NC-G and CoP nanoparticles, and iv) rapid electron transfer between the catalytic centers and Nickle foam. This provides a new perspective to design efficient electrocatalysts for electrocatalytic 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.     

Co3O4 nanoparticles decorated Polypyrrole/carbon nanocomposite as efficient bi-functional electrocatalyst for electrochemical water splitting

An effective bi-functional electrocatalyst of Co₃O₄/Polypyrrole/Carbon (Co₃O₄/Ppy/C) nanocomposite was prepared through a simple dry chemical method and used to catalyze the oxygen evolution reaction (OER) and hydrogen evolution reaction (HER). Three types of carbon support as Vulcan carbon, reduced graphite oxide (RGO) and multi-walled carbon nanotubes (MCNTs) were used to study the influence on electrochemical reactions. Spherical shaped Co₃O₄ nanoparticles with 8–10 nm was found uniformly distributed on Ppy/C composite, which were analyzed by X-ray diffraction and transmission electron microscopy techniques. Amongst, Co₃O₄/Ppy/MWCNT shows improved bifunctional electrocatalytic activity towards both OER and HER with relatively low over potential (340 mV vs. 490 mV at 10 mA cm⁻²) and Tafel slope (87 vs. 110 mV dec⁻¹). In addition to that, MWCNT supported Co₃O₄/Ppy nanocomposite exhibits good electronic conductivity and electrochemical stability up to 2000 potential cycles. The results clearly indicate that the Co₃O₄/Ppy/MWCNT nanocomposite could be the promising bi-functional electrocatalyst for efficient water electrolysis.     

Lanthanum doped copper oxide nanoparticles enabled proficient bi-functional electrocatalyst for overall water splitting

The need for a clean and an environmentally non-degrading sustainable energy resource has grown worldwide due to the huge depletion of other fuel sources, as a result, production of hydrogen by electrochemical water splitting is considered as a potential answer to this pertaining need. However, development of low-cost electrocatalyst as a replacement for Pt and RuO₂ for both Hydrogen Evolution Reaction (HER) and Oxygen Evolution Reaction (OER) remains a significant challenge for the production of hydrogen at a larger scale. This study presents the synthesis of non-noble metal-based lanthanum doped copper oxide nanoparticles as a potential bi-functional electrocatalyst for overall water splitting in alkaline electrolyte. The optimized 1% lanthanum (La) doped CuO electrocatalyst exhibits outstanding OER and HER activity in 1.0 M KOH electrolyte posting a potential of 1.552 V vs RHE for OER and −0.173 V vs RHE for HER at a current density of ~10 mAcm⁻². Significantly, the functional bi-catalyst exhibits a low cell voltage of 1.6 V to achieve overall water splitting at a current density of 10 mAcm⁻² along with long-term stability of 13.5 h for a cell voltage of 2.25 V at a constant current density of 30 mAcm⁻² with only 20% initial current lose after 13.5 h. The results demonstrate that the incorporation of the rare-earth element onto CuO nanoparticles has made it a viable high-end non-noble electrocatalyst for overall water splitting.     

Porous Co2P film coated on carbon fiber as highly performance electrocatalyst toward overall water splitting

Designing porous active materials and enhancing their contact with conductive substrates is an effective strategy to improve electrolytic water splitting performance of noble metal-free catalysts. Herein, a facile nanostructured electrode, composed of porous Co₂P films coated on carbon fiber (CF@P–Co₂P), is designed and prepared. The unique three-dimensional interconnected pore structure of Co₂P and the close contact between porous Co₂P and CF not only increase specific surface areas to expose abundant catalytic sites but also stimulate the transport of electron, mass and gaseous products in catalytic process. Benefit from the reasonable electrode structure, the self-supported CF@P–Co₂P electrodes present perfect performance with only needing overpotentials of 107.7/175.5/141.8 mV for hydrogen evolution reaction (HER) in acidic/neutral/alkaline solution and 269.4 mV for oxygen evolution reaction (OER) in alkaline solution to get current density of 20 mA cm^?2. In addition, alkaline electrolyzer equipped with CF@P–Co₂P bifunctional electrodes only needs a cell voltage of 1.657 V to get water-splitting current density of 20 mA cm^?2. Even better, the electrolyzer can continuously electrolyze over 50 h with negligibly decreasing current density and the Faraday efficiency is close to 100% toward both HER and OER.     

Origin of the overall water splitting activity over Rh/Cr2O3@ anatase TiO2 following UV-pretreatment

Anatase TiO₂ has long been known to be one of the best photocatalysts. Its conduction band potential is thermodynamically allowed to drive a diverse range of photooxidation reactions. However, anatase TiO₂ cannot oxidize water into oxygen in photocatalytic overall water splitting that involves multi-hole transfers. In the present study, a simple pretreatment of anatase TiO₂ with highly-intense UV irradiation is demonstrated to enable overall water splitting upon loading with a Rh/Cr₂O₃ cocatalyst. Based on light-induced infrared absorption spectroscopy and time-resolved microwave conductivity, it is suggested that the efficient removal of deep hole traps permits free holes to possess a sufficiently strong oxidizing potential for water oxidation over Rh/Cr₂O₃@TiO₂.     

Mo/P doped NiFeSe as bifunctional electrocatalysts for overall water splitting

Designing high-efficiency catalysts for overall water splitting is critical to reduce the cost of hydrogen fuel as a clean and renewable energy source in future society. In this work, a Mo-, P-codoped NiFeSe was successfully synthesized on nickel foam (NF) by one-step electrodeposition. Through the doping strategy, the conductivity can be well promoted, and the production of nanosheets on the catalyst surface and active phases during hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) provided much more active sites, which leaded to efficient HER/OER performances of as-synthesized Mo-, P-codoped NiFeSe catalysts, i.e., a low overpotential of 100 mV/200 mV at current density of 10 mA cm⁻² in 1.0 M KOH with stability of 95 h/60 h, respectively. It only required 1.53 V to deliver a current density of 10 mA cm⁻² in overall water splitting and maintained outstanding durability for 100 h. This work is beneficial to future design of high efficient and low-cost bifunctional catalysts for overall water splitting.     

Combustion-derived BaNiO3 nanoparticles as a potential bifunctional electrocatalyst for overall water splitting

Electrochemical water electrolyser though an assuring solution for clean hydrogen production, the sluggish kinetics and high cost of existing precious metal electrocatalyst remains a barrier to its effective utilization. Herein, solution combustion route derived perovskite type barium nickelate (BaNiO₃) nanoparticles were developed and studied for their bifunctional electrocatalytic properties towards overall water splitting. The unannealed BaNiO₃ nanoparticles exhibited the highest OER and HER activity with overpotentials 253 mV and 427 mV respectively to attain 10 mAcm⁻² in 1.0 M KOH. Using unannealed BaNiO₃ as a bifunctional electrocatalyst in a two-electrode alkaline electrolyser, the cell was able to achieve the benchmark current density at a low cell voltage of 1.82 V. Impressively the setup's electrocatalytic performance improved 4.9% after continuous overall water splitting for 24 h at 30 mAcm⁻². Therefore, BaNiO₃ nanoparticles can be a low-cost and efficient alternative for noble metal electrocatalysts for clean H₂ production.     

Photocatalytic overall water splitting by Z-scheme g-C3N4/BiFeO3 heterojunction

Solar water splitting by photocatalysis in the absence of sacrificial agent has been identified as a promising approach to produce green hydrogen. Increasing photocatalytic efficiency is the core issue in this process. Forming heterojunctions is one potential solution to improve photoactivity. Herein, we successfully synthesized several g-C₃N₄/BiFeO₃ composites containing different mass ratio of g-C₃N₄ by an uncomplicated and cost-effective method. The composite samples exhibited remarkably enhanced photocatalytic performance compared with the bare BiFeO₃ and g-C₃N₄. The highest hydrogen production rate obtained is ~ 160.75 μmol h⁻¹.g-¹ under UV irradiation and ~23.31 μmol h⁻¹.g-¹ under visible light irradiation. This enhanced photocatalytic activity is attributed to the synergistic effect of the junction and Z-scheme charge transfer mechanism between BiFeO₃ and g-C₃N₄, which can effectively accelerate the separation of photogenerated electron-hole pairs and also capability of carrying out redox reaction.     

Embedding Co2P nanoparticles into co-doped carbon hollow polyhedron as a bifunctional electrocatalyst for efficient overall water splitting

The reasonable design and construction of non-precious metal electrocatalysts with low cost and high performance is critical for the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). Herein, a facile polymerization-pyrolysis method is proposed to encapsulate Co₂P nanoparticles in co-doped hollow carbon shell by using ZIF-67 and P-containing polymers as precursor. The unique construction not only effectively prevents nanoparticles from detaching, showing good stability after long-term testing, but also provides abundant active sites, large surface areas and large pore volumes, enabling the electrolyte and electrode material to full contact. As expected, the Co₂P/NPSC-800 performs superior HER performance with low overpotential of 173 mV at 10 mA cm⁻² and excellent stability of 88% retention for 35 h and OER performance with low overpotential of 320 mV at 10 mA cm⁻², which endows Co₂P/NPSC-800 with good catalytic activity in overall water splitting. Furthermore, density functional theory (DFT) calculations reveal that the metallic property and the decreased reaction barriers of Co₂P can promote the catalytic reactions. This work offers an effective route in synthesizing other transition metal phosphides with high catalytic properties.     

Bimetallic metal-organic framework derived electrocatalyst for efficient overall water splitting

The development of bifunctional catalysts that can be applied to both hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) is widely regarded as a key factor in the production of sustainable hydrogen fuel by electrochemical water splitting. In this work, we present a high-performance electrocatalyst based on nickel-cobalt metal-organic frameworks for overall water splitting. The as-obtained catalyst shows low overpotential to reaches the current density of 10 mA cm⁻² with 249 mV for OER and 143 mV for HER in alkaline media, respectively. More importantly, when the electrolyzer was assembled with the as-prepared catalyst as anode and cathode simultaneously, it demonstrates excellent activity just applies a potential of 1.68 V to achieve 10 mA cm⁻² current density for overall water splitting.     

ZIF-L-Co@carbon fiber paper composite derived Co/Co3O4@C electrocatalyst for ORR in alkali/acidic media and overall seawater splitting

Green and clean energy technologies, including fuel cells, metal-air batteries, water splitting et al., are becoming more significant for our lives. Oxygen reduction reaction (ORR), hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) are key reaction processes for fuel cells, metal-air batteries and water splitting. Therefore, it is highly desirable to design a multifunctional catalyst, which owns catalytic performance under a widely applied range. Herein, we demonstrate a novel multifunctional catalyst (Co/Co₃O₄@C) by carbonizing a composite material constructed of zeolite imidazolate framework and carbon fiber paper (ZIF-L-Co@CP). It is a carbon-based material containing metallic Co and Co₃O₄ as a low-cost and effective catalyst toward the ORR and overall water splitting. For ORR, the Co/Co₃O₄@C catalyst shows high half-wave potential in both alkaline and acidic media, 0.823 V for 0.1 M KOH and 0.672 V for 0.1 M HClO₄. More importantly, it exhibits good catalytic activities of hydrogen and oxygen evolutions to perform overall splitting in actual seawater.     

Uniform cobalt nanoparticles embedded in nitrogen-doped graphene with abundant defects as high-performance bifunctional electrocatalyst in overall water splitting

Co nanoparticles with uniform size (about 5 nm) embedded in N-doped graphene (Co-NG) were explored in this work. The introduction of a second carbon source of citric acid during synthesis prevented the Co atoms from growing up, thus regulating the size of the cobalt nanoparticles. N atoms in N-doped graphene had more lone-pair electrons, making it easier to capture electrons from hydrated ions, and facilitating the dynamics procedure of HER. Furthermore, N dopant rendered larger positive charge density on the adjacent carbon atoms, which was conducive to OER and HER. At 10 mA cm^?2 of the current density, the Co-NG/CC catalyst's overvoltage of HER was 78 mV, approaching that of 20% Pt/C (59 mV), an efficient precious metal electrocatalyst for HER, while its overvoltage of OER was about 225 mV, 12.5% lower than that of RuO₂ (257 mV, a common precious metal oxide OER electrocatalyst). In addition, this Co-NG/CC composite bifunctional catalyst displayed good electrochemical stability in alkali solution and might be designed as a dual-function catalyst in the application of overall water splitting. The cell voltage of Co-NG/CC//Co-NG/CC was only 1.66 V, approaching to that of full precious metal cell of Pt/C//RuO₂ (1.52 V), and revealing the good commercial application prospects of this composite bifunctional catalyst.     

Hydrogen production via highly efficient electrocatalyst based on 3D NixCo1-x(OH)2/NiFe-AM induce overall water splitting

The main factors limiting water splitting producing hydrogen production are overpotential, activity and persistence of electrocatalysts. Herein, a novel Ni_xCo_1-x(OH)₂ coupled with NiFe amorphous compound array growing on nickel foam substrate (expressed as Ni_xCo_1-x(OH)₂/NiFe-AM) was developed by facile hydrothermal and electrodeposition methods. Significantly, Ni_xCo_1-x(OH)₂/NiFe-AM with this unique structural exhibits superior activity and stability in the two half reactions of water electrolysis. In addition, when tested in an alkaline electrolyte with a current density of 10 mA cm⁻², the overpotentials of HER and OER was 157 mV and 196 mV (60 mA cm⁻²), respectively. The stability can up to 60 h. These test results show through constructing hierarchical nano-thron architecture enhanced electrocatalytic activity to produce hydrogen and oxygen.     

N,S co-doped NiCo2O4@CoMoO4/NF hierarchical heterostructure as an efficient bifunctional electrocatalyst for overall water splitting

Electrocatalytic overall water splitting technology has received considerable attention in recent years. The fabrication of low-cost, earth-rich and potent bifunctional electrocatalysts is vital for hydrogen evolution (HER) and oxygen evolution reactions (OER). Herein, the N and S co-doped NiCo₂O₄@CoMoO₄ heterostructures (N, S–NCO@CMO₄₀₀) are fabricated by CVD and hydrothermal methods. N and S atoms as auxiliary active centers can increase the activity of Ni, Co and Mo atoms at the same time. Hierarchical heterostructures generate more interfaces to accelerate mass transfer and enlarge the electrochemical surface area, which greatly enhances the catalytic activity. The catalyst displays outstanding OER performance. The overpotentials of OER and HER are 165 and 100 mV at a current density of 10 mA cm^?2, respectively. More importantly, the N, S–NCO@CMO₄₀₀-based water splitting cell has a low voltage of 1.46 V at 10 mA cm^?2. Furthermore, the N, S–NCO@CMO₄₀₀ runs for 120 h in stable operation. This work provides new ideas for the design of hierarchical heterostructures with two-element incorporation.     

Sulfuration of hierarchical Mn-doped NiCo LDH heterostructures as efficient electrocatalyst for overall water splitting

Constructing efficient bifunctional electrocatalysts for both cathode and anode is of great importance for obtaining green hydrogen by water splitting. Herein, sulfuration of hierarchical Mn-doped NiCo LDH heterostructures (Mn–NiCoS₂/NF) is constructed as a bifunctional electrocatalyst for oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) via a facile hydrothermal-annealing strategy. Mn–NiCoS₂/NF shows an overpotential of 310 mV at 50 mA cm⁻² for OER and 100 mV at 10 mA cm⁻² for HER in 1.0 M KOH. Moreover, only 1.496 V@10 mA cm⁻² is required for overall water splitting by using Mn–NiCoS₂/NF as catalyst dual electrodes in a two-electrode system. The excellent performance of Mn–NiCoS₂/NF should be attributed to the ameliorative energy barriers of adsorption/desorption for HO⁻/H₂O through the modification of electronic structure of NiCo basal plane by Mn-doping and the acceleration of water dissociation steps via rich delocalized electron inside sulfur vacancies. The construction of hierarchical Mn–NiCoS₂/NF heterostructures provides new prospects and visions into developing efficient-advanced electrocatalysts for overall water splitting.     

Structural engineering of hierarchically hetestructured Mo2C/Co conformally embedded in carbon for efficient water splitting

Developing low-cost and high efficient electrocatalysts for both oxygen and hydrogen evolution reaction in an alkaline electrolyte toward overall water splitting is still a significant challenge. Here, a novel hierarchically heterostructured catalyst composed of ultrasmall Mo₂C and metallic Co nanoparticles confined within a carbon layer is produced by a facile phase separation strategy. During thermal reduction of CoMoO₄ nanosheets in CO ambient, in-situ generated nanoscale Co and ultrafine Mo₂C conformally encapsulated in a conductive carbon layer. In addition, some carbon nanotubes catalyzed by Co nanoparticles vertically grew on its surface, creating 3D interconnected electron channels. More importantly, the integrated C@Mo₂C/Co nanosheets assembled into the hierarchical architecture, providing abundant active surface and retaining the structural integrity. Benefiting from such unique structure, the constructed hierarchical heterostructure shows low overpotentials of 280 mV and 145 mV to reach a current density of 10 mA cm⁻² for OER and HER in an alkaline electrolyte. Furthermore, the symmetrical electrolyzer assembled with catalyst exhibits a small cell voltage of 1.67 V at 10 mA cm⁻² in addition to outstanding durability, demonstrating the great potential as a high efficient bifunctional electrocatalyst for overall water splitting.     

Efficient overall water splitting using nickel boride-based electrocatalysts

Currently there is tremendous interest in the discovery of low cost and efficient electrocatalysts for the oxygen evolution reaction (OER) and the hydrogen evolution reaction (HER). In this work, iron-doped nickel boride (Fe_xNi_1-xB) and nickel boride (NiB) were successfully grown on 3D self-supporting graphene (SSG) electrodes via a one-step reduction approach. The Fe_0.2Ni_0.8B/SSG electrode required a very low overpotential of only 263 mV for OER (the best OER activity achieved to date for a metal boride). NiB/SSG showed modest OER performance but excellent HER activity. A water electrolyzer comprising Fe_0.2Ni_0.8B/SSG and NiB/SSG delivered a current density of 10 mA cm⁻² at a voltage of only 1.62 V. Further, the Fe_0.2Ni_0.8B/SSG and NiB/SSG catalysts showed excellent stability with no deactivation observed over 14 h of testing. Results demonstrate that nickel boride-based electrocatalysts are promising lost cost alternatives to precious metal-based electrocatalysts for OER, HER and overall water splitting.