With the development of clean hydrogen energy, the cost effective and high‐performance hydrogen evolution reaction (HER) electrocatalysts are urgently required. Herein, a green, facile, and ...time‐efficient Ru doping synergistic with air‐plasma treatment strategy is reported to boost the HER performance of CoNi‐layered double hydroxide (LDH) nanotube arrays (NTAs) derived from zeolitic imidazolate framework nanorods. The Ru doping and air‐plasma treatment not only regulate the oxygen vacancy to optimize the electron structure but also increase the surface roughness to improve the hydrophilicity and hydrogen spillover efficiency. Therefore, the air plasma treated Ru doped CoNi‐LDH (P‐Ru‐CoNi‐LDH) nanotube arrays display superior HER performance with an overpotential of 29 mV at a current density of 10 mA cm−2. Furthermore, by assembling P‐Ru‐CoNi‐LDH as both cathode and anode for two‐electrode urea‐assisted water electrolysis, a small cell voltage of 1.36 V is needed at 10 mA cm−2 and can last for 100 h without any obvious activity attenuation that showing outstanding durability. In general, the P‐Ru‐CoNi‐LDH can improve the HER performance from intrinsic electronic structure regulation cooperated with extrinsic surface wettability modification. These findings provide an effective intrinsic and extrinsic synergistic effect avenue to develop high performance HER electrocatalysts, which is potential to be applied to other research fields.
With the Ru‐doping in CoNi‐LDH, the air‐plasma treatment was tend to introduce appropriate O and N filling that can effectively regulate the electronic structure. What's more, the plasma treatment also increases the superwettability of the samples which facilitate the H2 spillover process. The synergistically regulation of the intrinsic electronic structure and interface wettability of CoNi‐LDH can boost the HER process.
Metal sulfides with excellent redox reversibility and high capacity are very promising electrode materials for sodium‐ion batteries. However, their practical application is still hindered by the poor ...rate capability and limited cycle life. Herein, a template‐based strategy is developed to synthesize nitrogen‐doped carbon‐coated Cu9S5 bullet‐like hollow particles starting from bullet‐like ZnO particles. With the structural and compositional advantages, these unique nitrogen‐doped carbon‐coated Cu9S5 bullet‐like hollow particles manifest excellent sodium storage properties with superior rate capability and ultra‐stable cycling performance.
Sodium storage: Bullet‐like Cu9S5 hollow particles coated with a layer of nitrogen‐doped carbon are synthesized by a template‐based strategy. Their structure and composition allow these carbon‐coated Cu9S5 hollow bullets to exhibit enhanced sodium storage performance in terms of excellent rate capability and ultra‐stable cycle life.
Electrocatalytic nitrate (NO3−) reduction reaction (NITRR) is an inspiring route for ammonia (NH3) synthesis at ambient condition. The metallic Cu‐based material with low cost and high activity is ...one of the most promising electrocatalysts for NITRR. However, due to the weaker atomic H*‐providing capacity, the produced intermediate—nitrite tends to accumulate on its surface, leading to unsatisfactory NH3 selectivity and Faradic efficiency (FE). Herein, a novel and facile O2/Ar plasma oxidation and subsequent electro‐reduction strategy is developed to synthesize a kind of metastable phase Cu. Excitingly, the metastable phase Cu demonstrates superior NITRR performance to conventional phase Cu with high NH4+ selectivity (97.8%) and FE (99.8%). Density function theory (DFT) calculations reveal that the upshift of the d‐band center to near the Fermi level in metastable phase Cu contributes to the enhanced activity, while the relatively strong adsorption of H* facilitates the conversion from NO2*/NO* to NOOH*/NOH* and thus ensures high selectivity and FE. Furthermore, when evaluated as cathode material in Zn‐NO3− battery, high power density (7.56 mW cm−2) and NH4+ yield (76 µmol h−1 cm−2) are achieved by the metastable phase Cu‐based battery.
Metastable phase Cu is synthesized by a novel O2/Ar plasma oxidation and subsequent electro‐reduction strategy. Due to the unique electronic structure, the metastable phase Cu exhibits superior electrocatalytic nitrate reduction performance to conventional phase Cu for ammonia synthesis. Specifically, the metastable phase Cu can significantly promote the coupling of NO2− with active H atoms, thus improving the performance of NH3 synthesis.
Antimony‐based electrode materials with high specific capacity have aroused considerable interest as anode materials for sodium‐ion batteries (SIBs). Herein, we develop a template‐engaged ...ion‐exchange method to synthesize Sb2Se3 microclips, and the as‐obtained Sb2Se3 microclips are further in situ coated with polypyrrole (PPy). Benefiting from the structural and compositional merits, these PPy‐coated Sb2Se3 microclips exhibit enhanced sodium‐storage properties in terms of high reversible capacity, superior rate capability, and stable cycling performance.
The PPy who loved me: PPy‐coated Sb2Se3 microclips are synthesized by a simple ion‐exchange method and subsequent in situ polypyrrole (PPy) coating. With their unique structural and composition, these PPy‐coated Sb2Se3 microclips exhibit enhanced sodium‐storage performance in terms of high specific capacity, excellent rate capability, and good cycling stability.
Electrode materials based on electrochemical conversion reactions have received considerable interest for high capacity anodes of sodium‐ion batteries. However, their practical application is greatly ...hindered by the poor rate capability and rapid capacity fading. Tuning the structure at nanoscale and increasing the conductivity of these anode materials are two effective strategies to address these issues. Herein, a two‐step ion‐exchange method is developed to synthesize hierarchical Cu‐doped CoSe2 microboxes assembled by ultrathin nanosheets using Co–Co Prussian blue analogue microcubes as the starting material. Benefitting from the structural and compositional advantages, these Cu‐doped CoSe2 microboxes with improved conductivity exhibit enhanced sodium storage properties in terms of good rate capability and excellent cycling performance.
Hierarchical Cu‐doped CoSe2 microboxes are synthesized by a two‐step sequential ion‐exchange strategy using Co–Co Prussian blue analogue microcubes as precursors. With their structural and compositional advantages, these unique Cu‐doped CoSe2 microboxes exhibit enhanced sodium‐storage performance in terms of high specific capacity, excellent rate capability, and long cycle life.
Electrochemical synthesis of hydrogen peroxide (H2O2) through 2e– oxygen reduction reaction is an effective approach to replace anthraquinone process. However, most reported electrocatalysts work ...effectively in alkaline medium in which H2O2 will easily decompose into water. It is still of great challenge to develop cost‐effective electrocatalysts with high activity and selectivity for electrocatalytic H2O2 production in acidic media. Herein, it is first theoretically demonstrated that the adsorption energy of OOH* intermediate on carbon can be optimized by embedding Co nanoparticles (Co NPs) and tuning oxygen‐containing functional groups, ensuring high activity and selectivity. Guided by density functional theory calculations, highly porous open carbon nanocages with embedded Co NPs are designed and synthesized by template‐engaged method. The pyrolysis temperature can effectively modulate the electronic and pore structure of carbon nanocages. Impressively, the optimized carbon nanocages synthesized at 700 °C (P‐Co@C‐700) with highest percentage of –C–O–C group and defects, largest specific surface area (1351 m2 g–1), and mesoporous structure exhibit high selectivity up to 94% toward H2O2 production in 0.1 m HClO4. Furthermore, the P‐Co@C‐700 nanocages display promising application for efficient electro‐Fenton degradation of model organic pollutant.
The density functional theory calculations predict that the adsorption energy of OOH* on carbon can be optimized by embedding Co nanoparticles and tuning oxygen‐containing functional groups for the electrosynthesis of H2O2. Guided by calculations, open carbon nanocages with optimized electronic and pore structures are synthesized, manifesting high selectivity up to 94% for H2O2 synthesis in 0.1 m HClO4.
Metal sulfide hollow nanostructures (MSHNs) have received intensive attention as electrode materials for electrical energy storage (EES) systems due to their unique structural features and rich ...chemistry. Here, we summarize recent research progress in the rational design and synthesis of various metal sulfide hollow micro‐/nanostructures with controlled shape, composition and structural complexity, and their applications to lithium ion batteries (LIBs) and hybrid supercapacitors (HSCs). The current understanding of hollow structure control, including single‐shelled, yolk‐shelled, multi‐shelled MSHNs, and their hybrid micro‐/nanostructures with carbon (amorphous carbon nanocoating, graphene and hollow carbon), is focused on. The importance of proper structural and compositional control on the enhanced electrochemical properties of MSHNs is emphasized. A relationship between structural and compositional engineering with improved electrochemical activity of MSHNs is sought, in order to shed some light on future electrode design trends for next‐generation EES technologies.
Metal sulfide hollow nanostructures are promising electrode materials for electrochemical energy storage devices including lithium‐ion batteries and hybrid supercapacitors. Recent progress in the synthesis of high‐quality metal sulfide hollow nanostructures is highlighted. Particular emphasis is given to the importance of rational design in structure/composition and their effects on electrochemical performances.
Ruthenium (Ru) is an ideal substitute to commercial Pt/C for hydrogen evolution reaction (HER). Reducing the size of Ru to clusters can greatly increase the utilization of atoms, however, over‐strong ...RuH binding will be brought about. Additionally, the water dissociation ability of Ru clusters is unfavorable, leading to unsatisfactory activity in alkaline and neutral HER. Herein, a rational and versatile design strategy is proposed by exploring supports with both high work function and facilitated water dissociation ability to boost the pH‐universal HER activity of Ru clusters. As exemplified by Mo2C, density functional calculations verify that the introduction of Mo2C support can optimize the hydrogen adsorption energy and promote the kinetics of water dissociation. Guided by theoretical calculations, heterostructured Mo2C nanoparticles‐Ru clusters anchored carbon spheres (Mo2C‐Ru/C) are designed and prepared. A low overpotential of 22 mV at 10 mA cm−2 and a small Tafel slope of 25 mV dec−1 in alkaline solution is demonstrated by Mo2C‐Ru/C. The Mo2C‐Ru/C also exhibits excellent activity in alkaline seawater, acidic, and neutral solutions. When assembling Mo2C‐Ru/C with Zn foil to construct an alkaline‐acid Zn‐H2O battery, the as‐fabricated battery presents high discharge power density and excellent stability for simultaneous generation of electricity and hydrogen (H2).
A rational and versatile design strategy is proposed by exploring supports with both high work function and facilitated water dissociation ability to boost the pH‐universal hydrogen evolution reaction (HER) activity of Ru clusters. Taking Mo2C as a typical model, theoretical calculations and experimental results verify that the introduction of Mo2C support can greatly improve the HER activity of Ru cluster.
Layered metal hydroxides (LMHs) are promising catalysts for oxygen evolution reaction. However, the hydrogen evolution reaction (HER) activity of LMHs is unsatisfactory due to their poor conductivity ...and limited active sites. Herein, taking Ni(OH)2 as demonstration, a novel “one stone five birds” plasma activation strategy synergistic with Ru single atoms (Ru SAs) doping is developed to boost the HER activity of Ni(OH)2 by constructing heterostructured β‐Ni(OH)2/Ni‐Ru SAs nanosheet arrays (NSAs). Benefiting from the structural/compositional features and optimized electronic state, the as‐obtained β‐Ni(OH)2/Ni‐Ru SAs NSAs exhibit splendid HER activity with a low overpotential of 16 mV at 10 mA cm−2 and a small Tafel slope of 21 mV dec−1 in alkaline solution. Excellent HER performance in alkaline seawater and neutral solutions are also demonstrated by the β‐Ni(OH)2/Ni‐Ru SAs NSAs. The plasma activation and Ru SAs doping play important roles in enhancing water adsorption and accelerating the kinetics of water dissociation. Density functional theory (DFT) calculations reveal that the introduction of Ru SAs in the system facilitates the generation of surface OH vacancies for providing more active sites as well as decreases the antibonding state density of the generated mid‐gap state for enhancing H adsorption strength toward the optimal range.
A novel “one stone five birds” plasma activation strategy synergistic with Ru single atoms (Ru SAs) doping is developed to boost the hydrogen evolution reaction (HER) activity of Ni(OH)2 by constructing heterostructured β‐Ni(OH)2/Ni‐Ru SAs nanosheet arrays (NSAs). The as‐obtained β‐Ni(OH)2/Ni‐Ru SAs NSAs exhibit splendid HER activity with a low overpotential of 16 mV and a small Tafel slope of 21 mV dec−1.
Hollow nanostructures have attracted increasing research interest in electrochemical energy storage and conversion owing to their unique structural features. However, the synthesis of hollow ...nanostructured metal phosphides, especially nonspherical hollow nanostructures, is rarely reported. Herein, we develop a metal–organic framework (MOF)‐based strategy to synthesize carbon incorporated Ni–Co mixed metal phosphide nanoboxes (denoted as NiCoP/C). The oxygen evolution reaction (OER) is selected as a demonstration to investigate the electrochemical performance of the NiCoP/C nanoboxes. For comparison, Ni–Co layered double hydroxide (Ni–Co LDH) and Ni–Co mixed metal phosphide (denoted as NiCoP) nanoboxes have also been synthesized. Benefiting from their structural and compositional merits, the as‐synthesized NiCoP/C nanoboxes exhibit excellent electrocatalytic activity and long‐term stability for OER.
Box clever: ZIF‐67@layered double hydroxide (LDH) nanoboxes are synthesized from highly uniform ZIF‐67 nanocubes through reaction with Ni(NO3)2 at room temperature. After phosphidation with NaH2PO2, the ZIF‐67@LDH nanoboxes are transformed into NiCoP/C nanoboxes, which have enhanced performance as an electrocatalyst for the oxygen evolution reaction (OER).
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