Dual Vacancies Confined in Nickel Phosphosulfide Nanosheets Enabling Robust Overall Water Splitting
TL;DR: In this article, a dual Ni,S vacancy engineering on 2D NiPS3 nanosheet was proposed for large-scale water splitting, which achieved small overpotentials of 124mV and 290mV at a current density of 10m-cm-2 for hydrogen evolution reaction (HER) and OER, respectively.
Abstract: 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.
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TL;DR: Porous phosphorized CoNi2 S4 yolkshell spheres (P-CoNi2S4 YSSs) were designed and synthesized by a combined hydrothermal sulfidation and gas-phase phosphorization strategy as discussed by the authors.
Abstract: 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.
129 citations
TL;DR: In this article , the challenges and future perspectives for anion-mixed water dissociation catalysts, including polyanionmixed and metal-free catalyst, are proposed and analyzed.
Abstract: This review introduces recent advances of various anion-mixed transition metal compounds (e.g., nitrides, halides, phosphides, chalcogenides, (oxy)hydroxides, and borides) for efficient water electrolysis applications in detail. The challenges and future perspectives are proposed and analyzed for the anion-mixed water dissociation catalysts, including polyanion-mixed and metal-free catalyst, progressive synthesis strategies, advanced in situ characterizations, and atomic level structure-activity relationship. Hydrogen with high energy density and zero carbon emission is widely acknowledged as the most promising candidate toward world's carbon neutrality and future sustainable eco-society. Water-splitting is a constructive technology for unpolluted and high-purity H2 production, and a series of non-precious electrocatalysts have been developed over the past decade. To further improve the catalytic activities, metal doping is always adopted to modulate the 3d-electronic configuration and electron-donating/accepting (e-DA) properties, while for anion doping, the electronegativity variations among different non-metal elements would also bring some potential in the modulations of e-DA and metal valence for tuning the performances. In this review, we summarize the recent developments of the many different anion-mixed transition metal compounds (e.g., nitrides, halides, phosphides, chalcogenides, oxyhydroxides, and borides/borates) for efficient water electrolysis applications. First, we have introduced the general information of water-splitting and the description of anion-mixed electrocatalysts and highlighted their complementary functions of mixed anions. Furthermore, some latest advances of anion-mixed compounds are also categorized for hydrogen and oxygen evolution electrocatalysis. The rationales behind their enhanced electrochemical performances are discussed. Last but not least, the challenges and future perspectives are briefly proposed for the anion-mixed water dissociation catalysts.
41 citations
TL;DR: In this article , the challenges and future perspectives for anion-mixed water dissociation catalysts, including polyanionmixed and metal-free catalyst, are proposed and analyzed.
Abstract: This review introduces recent advances of various anion-mixed transition metal compounds (e.g., nitrides, halides, phosphides, chalcogenides, (oxy)hydroxides, and borides) for efficient water electrolysis applications in detail. The challenges and future perspectives are proposed and analyzed for the anion-mixed water dissociation catalysts, including polyanion-mixed and metal-free catalyst, progressive synthesis strategies, advanced in situ characterizations, and atomic level structure-activity relationship. Hydrogen with high energy density and zero carbon emission is widely acknowledged as the most promising candidate toward world's carbon neutrality and future sustainable eco-society. Water-splitting is a constructive technology for unpolluted and high-purity H2 production, and a series of non-precious electrocatalysts have been developed over the past decade. To further improve the catalytic activities, metal doping is always adopted to modulate the 3d-electronic configuration and electron-donating/accepting (e-DA) properties, while for anion doping, the electronegativity variations among different non-metal elements would also bring some potential in the modulations of e-DA and metal valence for tuning the performances. In this review, we summarize the recent developments of the many different anion-mixed transition metal compounds (e.g., nitrides, halides, phosphides, chalcogenides, oxyhydroxides, and borides/borates) for efficient water electrolysis applications. First, we have introduced the general information of water-splitting and the description of anion-mixed electrocatalysts and highlighted their complementary functions of mixed anions. Furthermore, some latest advances of anion-mixed compounds are also categorized for hydrogen and oxygen evolution electrocatalysis. The rationales behind their enhanced electrochemical performances are discussed. Last but not least, the challenges and future perspectives are briefly proposed for the anion-mixed water dissociation catalysts.
31 citations
23 Aug 2021
24 citations
TL;DR: In this paper , a dual P, S-anions modification strategy was developed to optimize the catalytic performance of CoMoO4 nanowire arrays to drive both oxygen and hydrogen evolution reactions (OER/HER).
18 citations
References
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TL;DR: A hybrid catalyst constructed by iron and dinickel phosphides on nickel foams that drives both the hydrogen and oxygen evolution reactions well in base, and thus substantially expedites overall water splitting is reported, which outperforms the integrated iridium (IV) oxide and platinum couple (1.57 V).
Abstract: Water electrolysis is an advanced energy conversion technology to produce hydrogen as a clean and sustainable chemical fuel, which potentially stores the abundant but intermittent renewable energy sources scalably. Since the overall water splitting is an uphill reaction in low efficiency, innovative breakthroughs are desirable to greatly improve the efficiency by rationally designing non-precious metal-based robust bifunctional catalysts for promoting both the cathodic hydrogen evolution and anodic oxygen evolution reactions. We report a hybrid catalyst constructed by iron and dinickel phosphides on nickel foams that drives both the hydrogen and oxygen evolution reactions well in base, and thus substantially expedites overall water splitting at 10 mA cm−2 with 1.42 V, which outperforms the integrated iridium (IV) oxide and platinum couple (1.57 V), and are among the best activities currently. Especially, it delivers 500 mA cm−2 at 1.72 V without decay even after the durability test for 40 h, providing great potential for large-scale applications.
780 citations
TL;DR: Insight is provided into the defect mechanism in Co3O4 for OER in a dynamic way by observing the surface dynamic evolution process of defective electrocatalysts and identifying the real active sites during the electrocatalysis process.
Abstract: The exact role of a defect structure on transition metal compounds for electrocatalytic oxygen evolution reaction (OER), which is a very dynamic process, remains unclear. Studying the structure-activity relationship of defective electrocatalysts under operando conditions is crucial for understanding their intrinsic reaction mechanism and dynamic behavior of defect sites. Co3O4 with rich oxygen vacancy (VO) has been reported to efficiently catalyze OER. Herein, we constructed pure spinel Co3O4 and VO-rich Co3O4 as catalyst models to study the defect mechanism and investigate the dynamic behavior of defect sites during the electrocatalytic OER process by various operando characterizations. Operando electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV) implied that the VO could facilitate the pre-oxidation of the low-valence Co (Co2+, part of which was induced by the VO to balance the charge) at a relatively lower applied potential. This observation confirmed that the VO could initialize the surface reconstruction of VO-Co3O4 prior to the occurrence of the OER process. The quasi-operando X-ray photoelectron spectroscopy (XPS) and operando X-ray absorption fine structure (XAFS) results further demonstrated the oxygen vacancies were filled with OH• first for VO-Co3O4 and facilitated pre-oxidation of low-valence Co and promoted reconstruction/deprotonation of intermediate Co-OOH•. This work provides insight into the defect mechanism in Co3O4 for OER in a dynamic way by observing the surface dynamic evolution process of defective electrocatalysts and identifying the real active sites during the electrocatalysis process. The current finding would motivate the community to focus more on the dynamic behavior of defect electrocatalysts.
556 citations
TL;DR: A new N-anion-decorated Ni3 S2 material synthesized by a simple one-step calcination route is put forward, acting as a superior bifunctional electrocatalyst for the OER/HER for the first time.
Abstract: Developing non-noble-metal electrocatalysts with high activity and low cost for both the oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) is of paramount importance for improving the generation of H2 fuel by electrocatalytic water-splitting. This study puts forward a new N-anion-decorated Ni3 S2 material synthesized by a simple one-step calcination route, acting as a superior bifunctional electrocatalyst for the OER/HER for the first time. The introduction of N anions significantly modifies the morphology and electronic structure of Ni3 S2 , bringing high surface active sites exposure, enhanced electrical conductivity, optimal HER Gibbs free-energy (ΔGH* ), and water adsorption energy change (ΔGH2O* ). Remarkably, the obtained N-Ni3 S2 /NF 3D electrode exhibits extremely low overpotentials of 330 and 110 mV to reach a current density of 100 and 10 mA cm-2 for the OER and HER in 1.0 m KOH, respectively. Moreover, an overall water-splitting device comprising this electrode delivers a current density of 10 mA cm-2 at a very low cell voltage of 1.48 V. Our finding introduces a new way to design advanced bifunctional catalysts for water splitting.
522 citations
TL;DR: Transition metal phosphides (TMPs) have attracted growing interest as heterogeneous electrocatalysts for overall water splitting as discussed by the authors, and several strategies have been developed for preparing TMPs with enhanced HER or OER performance.
494 citations
TL;DR: Bridging the gap, to some extent, between precise design from theory and practical modulation in experiments, the proposed strategy extends defect engineering to a more sophisticated level for further unlocking the potential of catalytic performance enhancement.
Abstract: Defect engineering is widely applied in transition metal dichalcogenides (TMDs) to achieve electrical, optical, magnetic, and catalytic regulation. Vacancies, regarded as a type of extremely delica...
481 citations