Double functionalization of N-doped carbon carved hollow nanocubes with mixed metal phosphides as efficient bifunctional catalysts for electrochemical overall water splitting

Lv, Chaonan; Zhang, Lei; Huang, Xinhua; Zhu, Yuanxin; Zhang, Xin; Hu, Jin‐Song; Lu, Shih‐Yuan

doi:10.1016/j.nanoen.2019.103995

Cited by 115 publications

(46 citation statements)

References 69 publications

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“…[15][16][17][18] At present, noble Pt metal and Ir/Ru-based oxides are the benchmark electrocatalysts to speed up the HER and the OER, respectively. [19][20][21][22][23] Unfortunately, the tremella-like Ni 3 S 2 /MnS-O with abundant oxygen vacancies, which was favorable for HER and OER. [37] An in situ formation of {111} faceted Ni 3 S 2 on the surface of nickel foam toward HER and OER via a one-step hydrothermal process in a Na 2 S aqueous solution was also demonstrated.…”

Section: Introductionmentioning

confidence: 99%

Ultrathinning Nickel Sulfide with Modulated Electron Density for Efficient Water Splitting

Fei

Chen

Liu

et al. 2020

Advanced Energy Materials

271

140

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Developing nonprecious electrocatalysts via a cost‐effective methods to synergistically achieve high active sites exposure and optimized intrinsic activity remains a grand challenge. Here a low‐cost and scaled‐up chemical etching method is developed for transforming nickel foam (NF) into a highly active electrocatalyst for both the hydrogen evolution reaction (HER) and the oxygen evolution reaction (OER). The synthetic method involves a Na2S‐induced chemical etching of NF in the presence of Fe, leading to a growth of ultrathin Fe‐doped Ni3S2 arrays on the NF substrate (FexNi3‐xS2 @ NF). The combined experimental and theoretical investigations reveal that the incorporated Fe cations significantly modulate the morphology and the surface electron density of Ni3S2, and thus significantly boost the electrochemically active surface area, electron transfer, and optimize the hydrogen/water absorption free energy. The developed Fe0.9Ni2.1S2 @ NF requires overpotentials of only 72 mV at 10 mA cm−2 for HER and 252 mV at 100 mA cm−2 for OER in 1.0 m KOH, respectively, enabling an alkaline electrolyzer at a low cell voltage of 1.51 V to drive 10 mA cm−2 for overall water splitting. More broadly, this synthetic approach is very versatile and can be used to synthesize other ultrathin metal sulfides (e.g., Fe–Cu–S, Fe–Al–S, and Fe–Ti–S).

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Section: Introductionmentioning

confidence: 99%

Ultrathinning Nickel Sulfide with Modulated Electron Density for Efficient Water Splitting

Fei

Chen

Liu

et al. 2020

Advanced Energy Materials

271

140

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“…[61] Therefore, it is no surprise that the NiÀ CoÀ FeÀ P@CC exhibits the fourth-rank catalytic activity with η 10 = 302 mV, which may be ascribed to a lack of nanopores necessary for accelerating access to the interior active sites as well as the escape of product bubbles ( Figure S8). [38] Next, we clarify the influence of cobalt-induced intrastructural enhancement and electronic structure modulation on the OER activity. The NiÀ FeÀ P@CC-E-15 sample exhibited the lowest OER performance with an overpotential of 344 mV at 10 mA cm À 2 , which can be attributed to the following: DFT calculations and DSC analyses demonstrated that the introduction of cobalt ions can lead to the formation of NiÀ CoÀ Fe PBA, thereby enhancing stability and mechanical strength, which are particularly important for maintaining morphology during thermal phosphorization.…”

Section: Resultsmentioning

confidence: 99%

“…[60] Three component signals of pyridinic-N (398.5 eV), pyrrolic-N (400.1 eV), and quaternary-N (401.3 eV) as seen in Figure 6f, confirm N-doping in the obtained carbon matrix; this is conducive to enhancing the conductibility of the sample, which in turn promotes the OER activity. [38] The OER activities of the catalyst products were studied in a 1.0 m KOH solution with a typical three-electrode system. To determine the cause of the enhanced OER efficiency in NiÀ CoÀ FeÀ P@CC-E-15, five reference catalysts were designed and developed.…”

Section: Resultsmentioning

confidence: 99%

“…Generally, the smaller the Tafel slope, the lower the required OER overpotential of the catalytic process under the same kinetic current density or apparent current density. [38] In Figure 7d, it can be seen that the resultant NiÀ CoÀ FeÀ P@CC-E-15 presents an ultrasmall Tafel slope of 47 mV dec À 1 , lower than the other catalysts: 66 mV dec À 1 for NiÀ CoÀ FeÀ P@CC-E-18, 75 mV dec À 1 for NiÀ CoÀ FeÀ P@CC-E-12, 90 mV dec À 1 for NiÀ CoÀ FeÀ P@CC, 100 mV dec À 1 for Ni-CoÀ P@CC-E-15, 137 mV dec À 1 for NiÀ FeÀ P@CC-E-15, and 101 mV dec À 1 for RuO 2 . This confirms that NiÀ CoÀ FeÀ P@CC-E-15 possesses more advantageous charge transfer kinetics for a better OER reaction.…”

Section: Resultsmentioning

confidence: 99%

“…[35] In the last decade, Prussian blue analogue (PBA)-derived thermal phosphorization strategies have been repeatedly demonstrated as feasible and excellent "best of both worlds" solutions for the preparation of mixed-metal phosphide chainmail catalysts. [36][37][38] On one hand, it is easy to introduce multiple metal species into the crystal structure of PBA materials by controllable displacement or adsorption; these metal species serve as the reaction precursors for the desired multicomponent TMPs. [39] On the other hand, cyanide-derived carbon layers formed in situ on the surfaces of the phosphides can inherit most of the rich porous structures of the PBA host materials and can exhibit excellent conductivities resulting from Ndoping.…”

Section: Introductionmentioning

confidence: 99%

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Increasing Electrocatalytic Oxygen Evolution Efficiency through Cobalt‐Induced Intrastructural Enhancement and Electronic Structure Modulation

Zhang

Zhu

et al. 2020

ChemSusChem

Self Cite

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Electrolytic water splitting using surplus electricity represents one of the most cost-effective and promising strategies for hydrogen production. The high overpotential of the oxygenevolution reaction (OER) caused by the multi-electron transfer process with a high chemical energy barrier, however, limits its competitiveness. Here, a highly active and stable OER electrocatalyst was designed through a cobalt-induced intrastructural enhancement strategy combined with suitable electronic structure modulation. A carved carbon nanobox was embedded with tri-metal phosphide from a uniform NiÀ CoÀ Fe Prussian blue analogue (PBA) nanocube by sequential NH 3 • H 2 O etching and thermal phosphorization. The sample exhibited an OER activity in an alkaline medium, reaching a current density of 10 mA cm À 2 at an overpotential of 182 mV and displayed a small Tafel slope of 47 mV dec À 1 , superior to the most recently reported OER electrocatalysts. Moreover, it showed impressive electrocatalytic durability, increasing by approximately 2.7 % of operating voltage after 24 h of continuous testing. The excellent OER activity and stability are ascribed to a favorable transfer of mass and charge provided by the porous carbon shell, synergistic catalysis between the three-component metal phosphides originating from appropriate electronic structure modulation, more exposed catalytic sites on the hollow structure, and chainmail catalysis resulting from the carbon protective layer. It is foreseen that this successfully demonstrated design concept can be easily extended to other heterogeneous catalyst designs.

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Rational Design of Transition Metal Phosphide‐Based Electrocatalysts for Hydrogen Evolution

Liu

Yang

et al. 2022

Adv Funct Materials

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Developing efficient and inexpensive electrocatalysts for the hydrogen evolution reaction (HER) is critical to the commercial viability of electrochemical clean energy technologies. Transition metal phosphides (TMPs), with the merits of abundant reserves, unique structure, tunable composition, and high electronic conductivity, are recognized as attractive HER catalytic materials. Nevertheless, the HER electrocatalytic activity of TMPs is still limited by various thorough issues and inherent performance bottlenecks. In this review, these issues are carefully sorted, and the corresponding reasonable explanations and solutions are elucidated on the basis of the HER catalytic activity origins of TMPs. Subsequently, highly targeted multiscale strategies to improve the HER performance of TMPs are comprehensively presented. Additionally, critical scientific issues for constructing high‐efficiency TMP‐based electrocatalysts are proposed. Finally, the HER reaction process, catalytic mechanism research, TMP‐based catalyst construction, and their application expansion are mentioned as challenges and future directions for this research field. Expectedly, this review offers professional and targeted guidelines for the rational design and practical application of TMP‐based HER catalysts.

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Double functionalization of N-doped carbon carved hollow nanocubes with mixed metal phosphides as efficient bifunctional catalysts for electrochemical overall water splitting

Cited by 115 publications

References 69 publications

Ultrathinning Nickel Sulfide with Modulated Electron Density for Efficient Water Splitting

Ultrathinning Nickel Sulfide with Modulated Electron Density for Efficient Water Splitting

Increasing Electrocatalytic Oxygen Evolution Efficiency through Cobalt‐Induced Intrastructural Enhancement and Electronic Structure Modulation

Rational Design of Transition Metal Phosphide‐Based Electrocatalysts for Hydrogen Evolution

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