Mixed bimetallic oxides offer great opportunities for a systematic tuning of electrocatalytic activity and stability. Here, we demonstrate the power of this strategy using well-defined thermally prepared Ir–Ni mixed oxide thin film catalysts for the electrochemical oxygen evolution reaction (OER) under highly corrosive conditions such as in acidic proton exchange membrane (PEM) electrolyzers and photoelectrochemical cells (PEC). Variation of the Ir to Ni ratio resulted in a volcano type OER activity curve with an unprecedented 20-fold improvement in Ir mass-based activity over pure Ir oxide. In situ spectroscopic probing of metal dissolution indicated that, against common views, activity and stability are not directly anticorrelated. To uncover activity and stability controlling parameters, the Ir–Ni mixed thin oxide film catalysts were characterized by a wide array of spectroscopic, microscopic, scattering, and electrochemical techniques in conjunction with DFT theoretical computations. By means of an in...

Molecular insight in structure and activity of highly efficient, low-Ir Ir-Ni oxide catalysts for electrochemical water splitting (OER)

Exploring earth-abundant electrocatalysts with excellent activity, robust stability, and multiple functions is crucial for electrolytic hydrogen generation. Porous phosphorized CoNi2 S4 yolk-shell spheres (P-CoNi2 S4 YSSs) were rationally designed and synthesized by a combined hydrothermal sulfidation and gas-phase phosphorization strategy. Benefiting from the strengthened Ni3+ /Ni2+ couple, enhanced electronic conductivity, and hollow structure, the P-CoNi2 S4 YSSs exhibit excellent activity and durability towards hydrogen/oxygen evolution and urea oxidation reactions in alkaline solution, affording low potentials of -0.135 V, 1.512 V, and 1.306 V (versus reversible hydrogen electrode) at 10 mA cm-2 , respectively. Remarkably, when used as the anode and cathode simultaneously, the P-CoNi2 S4 catalyst merely requires a cell voltage of 1.544 V in water splitting and 1.402 V in urea electrolysis to attain 10 mA cm-2 with excellent durability for 100 h, outperforming most of the reported nickel-based sulfides and even noble-metal-based electrocatalysts. This work promotes the application of sulfides in electrochemical hydrogen production and provides a feasible approach for urea-rich wastewater treatment.

Phosphorized CoNi 2 S 4 Yolk-Shell Spheres for Highly Efficient Hydrogen Production via Water and Urea Electrolysis

Electrolysis of seawater makes full use of this natural resource and continuously turns it into a clean fuel, hydrogen. Electrocatalysts for seawater electrolysis must maintain a steady-state operation without suffering from chloride corrosion. In this study, we report a three-dimensional structure metal phosphide electrocatalyst by depositing cobalt-doped Fe2P (Co-Fe2P) on Ni foam. Density functional theory calculations showed that Co-Fe2P was beneficial for the hydrogen evolution reaction (HER) because of its suitable H* adsorption. Thus, the as-prepared Co-Fe2P acted as an efficient bifunctional electrocatalyst, exhibiting enhanced electrocatalytic properties for both the oxygen evolution reaction (OER) and HER. Moreover, the simulated alkaline seawater was used to determine the optimum potential (1.69 V at 100 mA cm−2) required for seawater splitting using the as-synthesized electrocatalyst. This study proposes a novel material for electrocatalytic application.

Synthesis of 3D heterostructure Co-doped Fe2P electrocatalyst for overall seawater electrolysis

Graphene-based electrocatalysts: Hydrogen evolution reactions and overall water splitting

Design and construction of low-cost electrocatalysts with high catalytic activity and long-term stability is a challenging task in the field of catalysis. Metal-organic frameworks (MOF) are promising candidates as precursor materials in the development of highly efficient electrocatalysts for energy conversion and storage applications. This review starts with a summary of basic concepts and key evaluation parameters involved in the electrochemical water-splitting reaction. Then, different synthesis approaches reported for the cobalt-based Zeolitic imidazolate framework (ZIF-67) and its derivatives are critically reviewed. Additionally, several strategies employed to enhance the electrocatalytic activity and stability of ZIF-67-based electrocatalysts are discussed in detail. The present review provides a succinct insight into the ZIF-67 and its derivatives (oxides, hydroxides, sulfides, selenides, phosphide, nitrides, telluride, heteroatom/metal-doped carbon, noble metal-supported ZIF-67 derivatives) reported for oxygen evolution reaction (OER), hydrogen evolution reaction (HER), and overall water splitting applications. Finally, this review concludes with the associated challenges and the perspectives on developing the best economic, durable electrocatalytic materials. 

Critical Review, Recent Updates on Zeolitic Imidazolate Framework‐67 (ZIF‐67) and Its Derivatives for Electrochemical Water Splitting

Utilizing earth-abundant metals to design economical and efficient electrocatalysts for cathodic hydrogen evolution reaction (HER) and anodic oxygen evolution reaction (OER) is critical for acquiri...

Universal Strategy of Bimetal Heterostructures as Superior Bifunctional Catalysts for Electrochemical Water Splitting

Water electrolysis is an advanced and sustainable energy conversion technology used to generate H2 . However, the low efficiency of the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) hampers the overall water-splitting catalytic performance. Here, a hybrid catalyst was constructed from N-doped CoS2 nanoparticles on N,S-co-doped graphene nanosheets (N-CoS2 /G) using a facile method, and the catalyst exhibited excellent bifunctional activity. Introduction of N atoms not only promoted the adsorption of reaction intermediates, but also bridged the CoS2 nanoparticles and graphene to improve electron transfer. Moreover, using thiourea as both N- and S-source ensured synthesis of much smaller-sized nanoparticles with more surface active sites. Surprisingly, the N-CoS2 /G exhibited superior catalytic activity with a low overpotential of 260 mV for the OER and 109 mV for the HER at a current density of 10 mA cm-2 . The assembled N-CoS2 /G : N-CoS2 /G electrolyzer substantially expedited overall water splitting with a voltage requirement of 1.58 V to reach 10 mA cm-2 , which is superior to most reported Co-based bifunctional catalysts and other non-precious-metal catalysts. This work provides a new strategy towards advanced bifunctional catalysts for water electrolysis.

Nitrogen-Incorporated Cobalt Sulfide/Graphene Hybrid Catalysts for Overall Water Splitting

Confinement of fluorine anions in nickel-based catalysts for greatly enhancing oxygen evolution activity

Dual anions engineering on nickel cobalt-based catalyst for optimal hydrogen evolution electrocatalysis.

Exploring highly efficient electrocatalysts for both the hydrogen evolution reaction (HER) and the oxygen evolution reaction (OER) is of great significance for addressing energy and environmental crises. Vacancy engineering has been regarded as a promising way to optimize the catalytic activity of electrocatalysts. Herein, we put forward a conceptually new dual Ni,S vacancy engineering on 2D NiPS3 nanosheet (denoted as V-NiPS3 ) by a simple ball-milling treatment with ultrasonication. This material presents an ideal model for exploring the role of dual vacancies in improving the catalytic activity for overall water splitting. Structural analyses make clear that the formation of dual Ni,S vacancies regulates the electronic structure and catalytic active sites of NiPS3 nanosheet, leading to the superior HER/OER performance. Smaller overpotentials of 124 mV and 290 mV can be achieved at a current density of 10 mA cm-2 for HER and OER, respectively. The OER performance of V-NiPS3 is the best value among all state-of-the-art NiPS3 catalysts. In addition, the assembled two-electrode cell incorporating V-NiPS3 exhibits enhanced catalytic performance with a low cell voltage of 1.60 V at 10 mA cm-2 . This work offers a promising avenue to improve the electrocatalytic performance of the catalysts by engineering dual vacancies for large-scale water splitting.

Pengzuo Chen

Papers

Universal Strategy of Bimetal Heterostructures as Superior Bifunctional Catalysts for Electrochemical Water Splitting

Nitrogen-Incorporated Cobalt Sulfide/Graphene Hybrid Catalysts for Overall Water Splitting

Confinement of fluorine anions in nickel-based catalysts for greatly enhancing oxygen evolution activity

Dual anions engineering on nickel cobalt-based catalyst for optimal hydrogen evolution electrocatalysis.

Dual Vacancies Confined in Nickel Phosphosulfide Nanosheets Enabling Robust Overall Water Splitting