Electronic Redistribution: Construction and Modulation of Interface Engineering on CoP for Enhancing Overall Water Splitting

Modulating and constructing interface engineering is an efficient strategy to enhance catalytic activity for water splitting. Herein, a hybrid nanoarray structure of V‐CoP@a‐CeO₂, where “a” represents amorphous, integrated into carbon cloth is fabricated for water splitting. The synergy effect between V and CeO₂ can increase the electron density of Co atoms at active sites, further optimizing the Gibbs free energy of H* adsorption energy (ΔG_H*). Besides, V‐CoP@a‐CeO₂ possesses lower water adsorption/dissociation energies, enabling accelerated reaction kinetics in alkaline media. As expected, the V‐CoP@a‐CeO₂ exhibits superior performance toward the hydrogen evolution reaction and the oxygen evolution reaction. More importantly, a two‐electrode electrolyzer combined with an electrocatalyst of V‐CoP@ a‐CeO₂ only demands that voltages of electrolytic cell are 1.56 and 1.71 V to achieve the current densities of 10 and 100 mA cm^?2, respectively. This work provides guidance for the design or optimization of materials for water electrolysis and beyond.     

Porous Pd/NiFeOx Nanosheets Enhance the pH-Universal Overall Water Splitting

Modulating the morphology and chemical composition is an efficient strategy to enhance the catalytic activity for water splitting, since it is still a great challenge to develop a bifunctional catalyst for oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) over a wide pH range. Herein, Pd/NiFeO_x nanosheets are synthesized with tightly arranged petal nanosheets and uniform mesoporous structure on nickel foam (NF). The porous 2D structure yields a larger surface area and exposes more active sites, facilitating water splitting at all pH values. The overpotential of Pd/NiFeO_x nanosheets for OER is only 180, 169, and 310 mV in 1 m KOH, 0.5 m H₂SO₄, and 1 m phosphate-buffered saline (PBS) conditions at 10 mA cm⁻² current density, as well as excellent HER activity with ultralow overpotential in a wide pH range. When using porous Pd/NiFeO_x nanosheets as bifunctional catalysts for water splitting, it just required a cell voltage of 1.57 V to reach a current density of 20 mA cm⁻² with nearly 100% faradic efficiency in alkaline conditions, which is much lower than that of benchmark Pt/CǁRuO₂ (1.76 V) couples, along with the improving stability benefiting from the good corrosion resistance of the inner NiFeO_x nanosheets.     

Oriented Growth of ZIF‐67 to Derive 2D Porous CoPO Nanosheets for Electrochemical‐/Photovoltage‐Driven Overall Water Splitting

Hydrogen generation from water splitting driven by electric/solar energy is highly desirable, which requires efficient and robust bifunctional electrocatalysts for both hydrogen and oxygen evolution reactions. 2D porous hybrids with attractive chemical and structural properties are the first‐class candidates for water splitting, while control over efficient and modulable synthesis remains a huge challenge. This work demonstrates a zeolitic imidazolate framework‐67 (ZIF‐67) nanoplate self‐template approach to fabricate 2D porous oxygen‐incorporated cobalt phosphide (CoPO) ultrathin nanosheets. The synthesis starts with the oriented growth of ZIF‐67 nanoplates along [211] crystal plane, followed by oxidation/phosphorization processes for pore generation and O/P coincorporation in the hybrid. The resultant 2D porous CoPO nanosheets afford very small voltages of 1.52 and 1.98 V for overall water splitting at 10 and 200 mA cm^?2, respectively. This excellent bifunctionality further provides the basis for photovoltage‐driven water splitting at a Faradaic efficiency of 97.6%. These findings offer a general strategy for rational design and modulation of 2D porous catalysts for various electrocatalytic and other applications.     

Large‐Size,Porous, Ultrathin NiCoP Nanosheets for Efficient Electro/Photocatalytic Water Splitting

Porous ultrathin 2D catalysts are attracting great attention in the field of electro/photocatalytic hydrogen evolution reaction (HER) and overall water splitting. Herein, a universal pH‐controlled wet‐chemical strategy is reported followed by thermal and phosphorization treatment to prepare large‐size, porous and ultrathin bimetallic phosphide (NiCoP) nanosheets, in which graphene oxide is adopted as a template to determine the size of products. The thickness of the resultant NiCoP nanosheets ranges from 3.5 to 12.8 nm via delicately adjusting pH from 7.8 to 8.5. The thickness‐dependent electrocatalytic performance is evidenced experimentally and explained by computational studies. The prepared large‐size ultrathin NiCoP nanosheets show excellent bifunctional electrocatalytic activity for overall water splitting, with low overpotentials of 34.3 mV for HER and 245.0 mV for oxygen evolution reaction, respectively, at 10 mA cm^?2. Furthermore, the NiCoP nanosheets exhibit superior photocatalytic HER performance, achieving a high HER rate of 238.2 mmol h^?1 g^?1 in combination with commonly used photocatalyst CdS, which is far superior to that of Pt/CdS (81.7 mmol h^?1 g^?1). All these results demonstrate large‐size porous ultrathin NiCoP nanosheets as an efficient and multifunctional electro/photocatalyst for water splitting.     

Engineering an Earth‐Abundant Element‐Based Bifunctional Electrocatalyst for Highly Efficient and Durable Overall Water Splitting

The simultaneous and efficient evolution of hydrogen and oxygen with earth‐abundant, highly active, and robust bifunctional electrocatalysts is a significant concern in water splitting. Herein, non‐noble metal‐based Ni–Co–S bifunctional catalysts with tunable stoichiometry and morphology are realized. The engineering of electronic structure and subsequent morphological design synergistically contributes to significantly elevated electrocatalytic performance. Stable overpotentials (η₁₀) of 243 mV (vs reversible hydrogen electrode) for oxygen evolution reaction (OER) and 80 mV for hydrogen evolution reaction (HER), as well as Tafel slopes of 54.9 mV dec^?1 for OER and 58.5 mV dec^?1 for HER, are demonstrated. In addition, density functional theory calculations are performed to determine the optimal electronic structure via the electron density differences to verify the enhanced OER activity is related to the Co top site on the (110) surface. Moreover, the tandem bifunctional NiCo₂S₄ exhibit a required voltage of 1.58 V (J = 10 mA cm^?2) for simultaneous OER and HER, and no obvious performance decay is observed after 72 h. When integrated with a GaAs solar cell, the resulting photoassisted water splitting electrolyzer shows a certified solar‐to‐hydrogen efficiency of up to 18.01%, further demonstrating the feasibility of engineering protocols and the promising potential of bifunctional NiCo₂S₄ for large‐scale overall water splitting.     

Metal‐Organic Frameworks Derived Nanotube of Nickel–Cobalt Bimetal Phosphides as Highly Efficient Electrocatalysts for Overall Water Splitting

The design of highly efficient, stable, and noble‐metal‐free bifunctional electrocatalysts for overall water splitting is critical but challenging. Herein, a facile and controllable synthesis strategy for nickel–cobalt bimetal phosphide nanotubes as highly efficient electrocatalysts for overall water splitting via low‐temperature phosphorization from a bimetallic metal‐organic framework (MOF‐74) precursor is reported. By optimizing the molar ratio of Co/Ni atoms in MOF‐74, a series of Cox Niy P catalysts are synthesized, and the obtained Co4Ni1P has a rare form of nanotubes that possess similar morphology to the MOF precursor and exhibit perfect dispersal of the active sites. The nanotubes show remarkable hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) catalytic performance in an alkaline electrolyte, affording a current density of 10 mA cm^?2 at overpotentials of 129 mV for HER and 245 mV for OER, respectively. An electrolyzer with Co4Ni1P nanotubes as both the cathode and anode catalyst in alkaline solutions achieves a current density of 10 mA cm^?2 at a voltage of 1.59 V, which is comparable to the integrated Pt/C and RuO₂ counterparts and ranks among the best of the metal‐phosphide electrocatalysts reported to date.     

N‐, O‐, and S‐Tridoped Carbon‐Encapsulated Co9S8 Nanomaterials: Efficient Bifunctional Electrocatalysts for Overall Water Splitting

The development of highly active and stable earth‐abundant catalysts to reduce or eliminate the reliance on noble‐metal based ones in green and sustainable (electro)chemical processes is nowadays of great interest. Here, N‐, O‐, and S‐tridoped carbon‐encapsulated Co₉S₈ (Co₉S₈@NOSC) nanomaterials are synthesized via simple pyrolysis of S‐ and Co(II)‐containing polypyrrole solid precursors, and the materials are proven to serve as noble metal‐free bifunctional electrocatalysts for water splitting in alkaline medium. The nanomaterials exhibit remarkable catalytic performances for oxygen evolution reaction in basic electrolyte, with small overpotentials, high anodic current densities, low Tafel slopes as well as very high (nearly 100%) Faradic efficiencies. Moreover, the materials are found to efficiently electrocatalyze hydrogen evolution reaction in acidic as well as basic solutions, showing high activity in both cases and maintaining good stability in alkaline medium. A two‐electrode electrolyzer assembled using the material synthesized at 900 °C (Co₉S₈@NOSC‐900) as an electrocatalyst at both electrodes gives current densities of 10 and 20 mA cm^?2 at potentials of 1.60 and 1.74 V, respectively. The excellent electrocatalytic activity exhibited by the materials is proposed to be mainly due to the synergistic effects between the Co₉S₈ nanoparticles cores and the heteroatom‐doped carbon shells in the materials.     

Novel Iron/Cobalt‐Containing Polypyrrole Hydrogel‐Derived Trifunctional Electrocatalyst for Self‐Powered Overall Water Splitting

Development of efficient, low‐cost, and durable electrocatalysts for the oxygen reduction reaction (ORR), oxygen evolution reaction (OER), and hydrogen evolution reaction (HER) is of significant importance for many electrochemical devices, such as rechargeable metal–air batteries, fuel cells, and water electrolyzers. Here, a novel approach for the synthesis of a trifunctional electrocatalyst derived from iron/cobalt‐containing polypyrrole (PPy) hydrogel is reported. This strategy relies on the formation of a supramolecularly cross‐linked PPy hydrogel that allows for efficient and homogeneous incorporation of highly active Fe/Co–N–C species. Meanwhile, Co nanoparticles are also formed and embedded into the carbon scaffold during the pyrolysis process, further promoting electrochemical activities. The resultant electrocatalyst exhibits prominent catalytic activities for ORR, OER, and HER, surpassing previously reported trifunctional electrocatalysts. Finally, it is demonstrated that the as‐obtained trifunctional electrocatalyst can be used for electrocatalytic overall water splitting in a self‐powered manner under ambient conditions. This work offers new prospects in developing highly active, nonprecious‐metal‐based electrocatalysts in electrochemical energy devices.     

Molybdenum and Phosphorous Dual Doping in Cobalt Monolayer Interfacial Assembled Cobalt Nanowires for Efficient Overall Water Splitting

The necessity for better water splitting requires speedy development of efficient catalysts with high activity, long‐term stability, and cost effectiveness. In this work, a bifunctional catalyst originating from the interfacial assembly of a thin Mo,P‐codoped Co layer (≈50 nm) shelled Co nanowire (Co‐Mo‐P/CoNWs) network is fabricated via a facile approach. The catalyst exhibits low overpotentials of 0.08 and 0.27 V to reach a current response of 20 mA cm^?2 for the hydrogen evolution reaction and oxygen evolution reaction, respectively, together with long‐term stability in 1.0 m KOH medium. The outstanding performance is further demonstrated by a Co‐Mo‐P/CoNWs‐based electrolyzer, which enables a cell voltage of only 1.495 V to reach 10 mA cm^?2, superior to one derived from commercial (Pt/C + RuO₂/C) as well as to various reports recently published elsewhere. It is recognized that the formation of multiactive centers together with the increased active site number caused by Mo and P dual doping synergistically promote both hydrogen and oxygen evolution performance. Such a hybrid material opens a new approach for developing efficient and cost‐effective catalysts for water splitting application.     

Iron‐Doped Cobalt Monophosphide Nanosheet/Carbon Nanotube Hybrids as Active and Stable Electrocatalysts for Water Splitting

Developing earth‐abundant, active, and stable electrocatalysts for water splitting is a vital but challenging step for realizing efficient conversion and storage of sustainable energy. Here, a multiscale structure‐engineering approach to construct iron (Fe) doped cobalt monophosphide (CoP) hybrids for efficient electrocatalysis of water splitting is reported. A two‐step method is developed to synthesize CoP nanosheets with uniform Fe doping and hybridization with carbon nanotubes (CNTs). The nanostructuring, uniform doping, and hybridization with CNT afford efficient electrocatalysts comparable to Pt/C for hydrogen evolution reactions in acidic, neutral, and alkaline electrolytes. It is found that the Fe doping level has different effects on catalytic activities in different electrolytes. Furthermore, after in situ oxidization/hydrolysis of the phosphides to corresponding oxyhydroxides, the hybrid electrocatalysts exhibit better performances than the benchmark commercial Ir/C for catalyzing the oxygen evolution reaction. A two‐electrode alkaline water electrolyzer constructed with these hybrid electrocatalysts can afford a current density of 10 mA cm^?2 at a voltage of 1.5 V.     

3D Self‐Supported Fe‐Doped Ni2P Nanosheet Arrays as Bifunctional Catalysts for Overall Water Splitting

The development of highly efficient bifunctional electrocatalysts for both hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) is crucial for improving the efficiency of overall water splitting, but still remains challenging issue. Herein, 3D self‐supported Fe‐doped Ni₂P nanosheet arrays are synthesized on Ni foam by hydrothermal method followed by in situ phosphorization, which serve as bifunctional electrocatalysts for overall water splitting. The as‐synthesized (Ni_0.33Fe_0.67)₂P with moderate Fe doping shows an outstanding OER performance, which only requires an overpotential of ≈230 mV to reach 50 mA cm^?2 and is more efficient than the other Fe incorporated Ni₂P electrodes. In addition, the (Ni_0.33Fe_0.67)₂P exhibits excellent activity toward HER with a small overpotential of ≈214 mV to reach 50 mA cm^?2. Furthermore, an alkaline electrolyzer is measured using (Ni_0.33Fe_0.67)₂P electrodes as cathode and anode, respectively, which requires cell voltage of 1.49 V to reach 10 mA cm^?2 as well as shows excellent stability with good nanoarray construction. Such good performance is attributed to the high intrinsic activity and superaerophobic surface property.     

High‐Performance Metal‐Free Nanosheets Array Electrocatalyst for Oxygen Evolution Reaction in Acid

Development of low cost electrocatalysts with outstanding catalytic activity and stability for oxygen evolution reaction (OER) in acid is a major challenge to produce hydrogen energy from water splitting. Herein, a novel metal‐free electrocatalyst consisting of a oxygen‐functionalized electrochemically exfoliated graphene (OEEG) nanosheets array is reported. Benefitting from a vertically aligned arrays structure and introducing oxygen functional groups, the metal‐free OEEG nanosheets array exhibits superior electrocatalytic activity and stability toward OER with a low overpotential of 334 mV at 10 mA cm^?2 in acidic electrolyte. Such a high OER performance is thus far the best among all previously reported metal‐free carbon‐based materials, and even superior to commercial Ir/C catalysts (420 mV at 10 mA cm^?2) in acid. Characterization results and electrochemical measurements identify the COOH species in the OEEG acting as active sites for acidic OER, which is further supported by atomic‐scale scanning transmission electron microscopy imaging and electron energy‐loss spectroscopy. Density functional theory calculations reveal that the reaction pathway of dual sites that is mixed by zigzag and armchair edges (COOH‐zig‐corner) is better than the pathway of single site.     

Epitaxial Heterogeneous Interfaces on N‐NiMoO4/NiS2 Nanowires/Nanosheets to Boost Hydrogen and Oxygen Production for Overall Water Splitting

Developing bifunctional efficient electrocatalysts for both the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) is in high demand for the development of overall water‐splitting devices. In particular, the electrocatalytic performance can be largely improved by designing positive nanoscale‐heterojunction with well‐tuned interfaces. Herein, a novel top‐down strategy is reported to construct the oxide/sulfide heterostructures (N‐NiMoO₄/NiS₂ nanowires/nanosheets) as a multisite HER/OER catalyst. Starting with the NiMoO₄ nanowires, nitridation in a controlled manner enables activation of Ni sites in NiMoO₄ and then yields oxide/sulfide heterojunction by directly vulcanizing the highly composition‐segregated N‐NiMoO₄ nanowires. The abundant epitaxial heterogeneous interfaces at atomic‐level facilitate the electron transfer from N‐NiMoO₄ to NiS₂, which further cooperate synergistically toward both the hydrogen and oxygen generation in alkali solution. Furthermore, with N‐NiMoO₄/NiS₂ grown carbon fiber cloth as the engineering electrode, the assembled N‐NiMoO₄/NiS₂–N‐NiMoO₄/NiS₂ system can deliver a current density of 10 mA cm^?2 with the cell voltage of 1.60 V in the water‐splitting reaction. This current density is 3.39 times higher than that of the Pt–Ir set (2.95 mA cm^?2). The excellent catalytic performance offered of N‐NiMoO₄/NiS₂ nanowires/nanosheets presents a great example to demonstrate the significance of interface engineering in the field of electrocatalysis.     

Ultrasmall Dispersible Crystalline Nickel Oxide Nanoparticles as High‐Performance Catalysts for Electrochemical Water Splitting

Ultrasmall, crystalline, and dispersible NiO nanoparticles are prepared for the first time, and it is shown that they are promising candidates as catalysts for electrochemical water oxidation. Using a solvothermal reaction in tert‐butanol, very small nickel oxide nanocrystals can be made with sizes tunable from 2.5 to 5 nm and a narrow particle size distribution. The crystals are perfectly dispersible in ethanol even after drying, giving stable transparent colloidal dispersions. The structure of the nanocrystals corresponds to phase‐pure stoichiometric nickel(ii ) oxide with a partially oxidized surface exhibiting Ni(iii ) states. The 3.3 nm nanoparticles demonstrate a remarkably high turn‐over frequency of 0.29 s^–1 at an overpotential of g = 300 mV for electrochemical water oxidation, outperforming even expensive rare earth iridium oxide catalysts. The unique features of these NiO nanocrystals provide great potential for the preparation of novel composite materials with applications in the field of (photo)electrochemical water splitting. The dispersed colloidal solutions may also find other applications, such as the preparation of uniform hole‐conducting layers for organic solar cells.     

Metal Boride‐Based Catalysts for Electrochemical Water‐Splitting: A Review

Electrocatalytic water‐splitting has gained a firm hold in the area of renewable hydrogen production owing to its integrative compatibility with intermittent energy sources. However, wide‐scale implementation of this technology demands discovery of new electrode materials that strike a good balance between efficiency, stability, and cost. In the pool of inexpensive electrodes capable of catalyzing hydrogen and oxygen evolution reactions, metal borides/borates have made a big splash in the last decade. However, the research in this family of electrocatalysts remains unorganized owing to the diversity of reports. This review summarizes the past and present research progress in metal borides/borates for electrocatalytic water‐splitting. The fundamental reasons for electrochemical behavior in different metal borides/borates are highlighted here, also including some comments regarding erroneous practices in the performance evaluation of metal borides/borates. Various strategies used to enhance the electrocatalytic performance of metal borides/borates are discussed in detail. Different methods evolved over the years for the synthesis of metal borides/borates are also discussed. Finally, an assessment of the commercial viability of metal borides/borates is made and future research directions are suggested.     

Boosting Activity on Co4N Porous Nanosheet by Coupling CeO2 for Efficient Electrochemical Overall Water Splitting at High Current Densities

Developing highly active nonprecious electrocatalysts with superior durability for both the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) is crucial to improve the efficiency of overall water splitting but remains challenging. Here, a novel superhydrophilic Co₄N‐CeO₂ hybrid nanosheet array is synthesized on a graphite plate (Co₄N‐CeO₂/GP) by an anion intercalation enhanced electrodeposition method, followed by high‐temperature nitridation. Doping CeO₂ into Co₄N can favor dissociation of H₂O and adsorption of hydrogen, reduce the energy barrier of intermediate reactions of OER, and improve the compositional stability, thereby dramatically boosting the HER performance while simultaneously inducing enhanced OER activity. Furthermore, the superhydrophilic self‐supported electrode with Co₄N‐CeO₂ in situ grown on the conductive substrate expedites electron conduction between substrate and catalyst, promotes the bubble release from electrode timely and impedes catalyst shedding, ensuring a high efficiency and stable working state. Consequently, the Co₄N‐CeO₂/GP electrode shows exceptionally low overpotentials of 24 and 239 mV at 10 mA cm^?2 for HER and OER, respectively. An alkaline electrolyzer by using Co₄N‐CeO₂/GP as both the cathode and anode requires a cell voltage of 1.507 V to drive 10 mA cm^?2, outperforming the Pt/C||RuO₂ electrolyzer (1.540 V@10 mA cm^?2). More significantly, the electrolyzer has extraordinary long‐term durability at a large current density of 500 mA cm^?2 for 50 h, revealing its potential in large‐scale applications.     

One‐Step Synthesis of CoS‐Doped β‐Co(OH)2@Amorphous MoS2+x Hybrid Catalyst Grown on Nickel Foam for High‐Performance Electrochemical Overall Water Splitting

Developing efficient and economical electrocatalysts for hydrogen evolution reaction and oxygen evolution reaction with readily available metals is one of the main challenges for large scale hydrogen/oxygen production. This study reports one step synthesis of cobalt and molybdenum hybrid materials for high performance overall water splitting. The binder‐free CoS‐doped β‐Co(OH)₂@amorphous MoS_2+x is coated on nickel foam (NF) to form 3D networked nanoplates that have large surface area and high durability for electrochemical reactions. The catalytic activity of electrocatalyst for hydrogen evolution is mainly attributed to the unsaturated sulfur site of amorphous MoS_2+x. Meanwhile, the CoS‐doped β‐Co(OH)₂ plays the major role in oxygen evolution. CoS‐doped β‐Co(OH)₂ and aMoS_2+x are strongly bound to each other due to CoS_x bridging. This CoS? Co(OH)₂@aMoS_2+x/NF hybrid exhibits excellent catalytic activity and stability for overall water splitting. For over 100 000 s the cell voltage required to achieve the current density of 10 mA cm^–2 is only 1.58 V, which is remarkably low among the commercially available electrocatalysts. The findings open up an easy and inexpensive method of large scale fabrication of bifunctional electrocatalysts for overall water splitting.     

High‐Performance Near‐Infrared Photodetector Based on Ultrathin Bi2O2Se Nanosheets

As an emerging 2D layered material, Bi₂O₂Se has shown great potential for applications in thermoelectric and electronics, due to its high carrier mobility, near‐ideal subthreshold swing, and high air‐stability. Although Bi₂O₂Se has a suitable band gap for infrared (IR) applications, its photoresponse properties have not been investigated. Here, high‐quality ultrathin Bi₂O₂Se sheets are synthesized via a low‐pressure chemical vapor deposition method. The thickness of 90% Bi₂O₂Se sheets is below 10 nm and lateral sizes mainly distribute in the range of 7–11 µm. In addition, it is found that triangular sheets largely lack “O” content, even only 0.2 for Bi₂O_0.2Se. The near‐IR photodetection performance of Bi₂O₂Se nanosheets is systematically studied by variable temperature measurements. The response time, responsivity, and detectivity can approach up to 2.8 ms, 6.5 A W^?1, and 8.3 × 10¹¹ Jones, respectively. Additionally, the critical performance parameters, including responsivity, rising time, and decay time, remain at almost the same level when the temperature is changed from 80 to 300 K. These phenomena are likely due to the fact that as‐grown ultrathin Bi₂O₂Se sheets have no surface trap states and shallow defect energy levels. The findings indicate ultrathin Bi₂O₂Se sheets have great potentials for future applications in ultrafast, flexible near‐IR optoelectronic devices.     

Bowtie‐Shaped NiCo2O4 Catalysts for Low‐Temperature Methane Combustion

Bowtie‐shaped NiCo₂O₄ nanostructures are prepared using a hydrothermal method. Variation of the synthesis parameters, including reaction time, additives, and calcination temperature, allows an understanding of the origin of the bowtie‐shaped structure to be developed. Methane oxidation experiments performed using temperature‐programed oxidation (TPO) show that the new materials, which do not contain precious metals, have excellent activity for low‐temperature methane combustion, with 100% conversion at ≈410 °C (gas hourly space velocity (GHSV): 90 000 mL (STP) g^?1 h^?1). The structure–activity relationships of the bowtie‐shaped nanostructures are explored.