A rhodium/silicon co-electrocatalyst design concept to surpass platinum hydrogen evolution activity at high overpotentials

Zhu, Lili; Lin, Haiping; Li, Youyong; Liao, Fan; Lifshitz, Y.; Sheng, Minqi; Lee, Shuit‐Tong; Shao, Mingwang

doi:10.1038/ncomms12272

Cited by 287 publications

(174 citation statements)

References 25 publications

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“…To better understand the HER catalytic activity of these samples, Tafel slopes are estimated (Figure 4b). [ 20 ] The Tafel slopes of Pt/C/NF, NCS@N‐rGO/NF, NCS@rGO/NF, and NCS/NF are determined to be 35.7, 52.0, 84.1, and 108.3 mV dec −1 respectively. As expected, Pt/C electrode has best HER activity, whereas NCS@N‐rGO/NF electrode exhibits better HER performance and activity than other samples.…”

Section: Resultsmentioning

confidence: 99%

Vertically Aligned NiCo₂S₄ Nanosheets Deposited on N‐Doped Graphene for Bifunctional and Durable Electrode of Overall Water Splitting

Lee

Pan

Gund

et al. 2020

Adv Materials Inter

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electrocatalysts, which contain both HER and OER activities, has advantages in terms of simplified symmetric cell design and reduced cost. [3] However, the practical applications of noble metal-based materials are still restricted due to high price, rarity, poor durability, and lopsided bifunctional activity.Recently, transition metal-based materials have been exploited as HER or OER electrocatalysts to replace existing noble metals. [4] Transitional metal sulfides (TMSs) consisting of ternary compounds exhibit the synergistic cooperation of the different components for high electrocatalytic activity. [5,6] Nevertheless, bifunctional activity and durability of TMSs still remain unsatisfactory for overall water splitting. [7] Moreover, the binderfree self-supported configuration can reduce the contact resistance between the current collector and the electrocatalysts, minimizing the loading of inactive species. [6,8] Herein, we design vertically aligned NiCo 2 S 4 nanosheets deposited on nitrogen-incorporated reduced graphene oxide (N-rGO) coated nickel foam (NCS@N-rGO/NF) for overall water splitting. The resulting binder-free free-standing electrodes exhibit the vertical growth of NiCo 2 S 4 nanosheets on the modified surface of the N-rGO/Ni foam, which ensures the exposure of the active sites and facile charge transfer. [9] Moreover, a rapid mass transport and facile access to active sites is accomplished by 3D interconnected porous structure. The electrocatalytic activity can be further improved due to the synergistic effects of the interaction between TMS with rGO in a hierarchical structure. [10] Furthermore, heteroatom-doped carbon materials such as N-rGO can improve the electron conductivity and electrolysis durability of TMSs. [11] Result and DiscussionThe binder-free NCS@N-rGO/NF electrodes were synthesized in three-steps as shown in Figure 1. First, rGO was coated on NF using a hydrothermal method at 393 K for 2 h. Then, N atoms were incorporated to fabricate N-rGO/NF electrode through chemical vapor deposition (CVD) using urea as N precursor. The CVD was performed at 623 and 773 K, successively, where urea is gasified at 623 K and adsorbed on rGO/NF, then N doping is done at 773 K. Finally, NiCo 2 S 4 nanosheets Developing non-noble metal electrocatalysts with high catalytic activity and stability is very important for practical water splitting technology. Herein, electrocatalytically active, bifunctional, and durable electrodes, are reported where NiCo 2 S 4 nanosheets deposited onto nitrogen-incorporated reduced graphene oxide (N-rGO) are assembled onto 3D Ni foam. These freestanding binder-free electrodes exhibit excellent bifunctional catalytic activity for both hydrogen evolution and oxygen evolution reactions in alkaline condition, as well as overall water splitting reaction measured in a two-electrode configuration. The cell voltage is as low as 1.63 V to achieve a current density of 10 mA cm −2 and this value is well preserved with negligible overpotential for more than 50 h. The results open ...

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Section: Resultsmentioning

confidence: 99%

Vertically Aligned NiCo₂S₄ Nanosheets Deposited on N‐Doped Graphene for Bifunctional and Durable Electrode of Overall Water Splitting

Lee

Pan

Gund

et al. 2020

Adv Materials Inter

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“…Meanwhile, the long‐term stability of water‐splitting reaction was also evaluated. However, evaluations of electrode have to take into account the fact that the small current densities (e. g., at 10 mA cm −2 ) is too low to fulfill usage requirements for the practical device, and the full water splitting at high current densities has received far less attention ,. Therefore, the durability at large current densities is also an important criterion and chronoamperometry measurement was performed at 100 and 200 mA cm −2 in 1 M KOH, respectively.…”

Section: Results and Disscussionmentioning

confidence: 99%

In‐situ Tailoring Cobalt Nickel Molybdenum Oxide Components for Overall Water‐Splitting at High Current Densities

Ren

Jin

et al. 2018

ChemElectroChem

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Developing non‐precious bifunctional electrocatalysts to drive the over water splitting that can operate well at high current densities (1,000 mA/cm2) is an urgent requirement for viable electrolysis of water. Transition metal oxides (TMO) have been intensely investigated as one of the most efficient oxygen evolution reaction (OER) catalysts. Unfortunately, their sluggish reaction kinetics towards hydrogen evolution reaction (HER) bring about poor overall performance. In this study, we perform a simple method to obtain the bifunctional TMO‐based electrocatalyst by in‐situ tailoring the components of cobalt nickel molybdenum oxide on nickel foam. By optimizing the annealing temperature and reaction atmosphere, we integrate HER‐active (CoMoNi) and OER‐active (CoMoOx) components together as bifunctional electrocatalysts for overall water splitting. Impressively, the as‐synthesized electrocatalyst shows the high electrocatalytic activity for both OER and HER, and exhibit a low cell voltage of 1.59 V at 10 mA cm−2 when applied as both the cathode and anode in alkaline solutions. Impressively, the bifunctional electrocatalysts work well at large current densities, even in the order of 1,000 mA cm−2 (only need the cell voltage of ∼2.03 V), and remain its activity more than 20 h. Such an outstanding performance should be mainly attributed to integrated high electronic conductivity, 3D self‐supported structure, and good compatibility between HER‐active and OER‐active components. This study shows a positive model for the design of more promising and practical catalysts for full water splitting.

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“…Hydrogen atom spillover (not to be confused with H2 spillover, which includes dissociation and is an important step for hydrogenation reactions and hydrogen storage) was recognized as phenomenon responsible for the promotion of Pt electrocatalytic activity towards the hydrogen evolution 47 years ago, for Pt supported on pyrolytic graphite [144]. Several experimental works contributed to the affirmation of Hads spillover as the important step in HER mechanism at Pt/C [145], Pt/transition-metal-oxide [146], Pt/Au [147], Pi/Ni [148], atomically-dispersed-Pt/WO3-x [149], Pd/Au [150], WO3·2H2O/WS2 [151], Rh/MoS2 [152], Rh/Si (although authors do not employ the term spillover) [153], Pd@Cu(II) phthalocyanine/MOF [69], and Ni/rGO interfaces [154,155]. Kinetic Monte-Carlo simulations were employed to investigate the impact of spillover rate on the rate of H2 production at Ni/rGO interface, using the model that was able to qualitatively reproduce the experimentally observed trends [155].…”

Section: Role Of the Metal-support Interfaces In Her Mechanismmentioning

confidence: 99%

Hydrogen Evolution Reaction - From Single Crystal to Single Atom Catalysts

Gutić¹,

Dobrota²,

Fako³

et al. 2020

Preprint

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Hydrogen evolution reaction (HER) is one of the most important reaction in electrochemistry. This is not only because it is the simplest way to produce high purity hydrogen and the fact that it is the side reaction in many other technologies. HER actually shaped current electrochemistry because it was in focus of active research for so many years (and it still is). The number of catalysts investigated for HER is immense, and it is impossible to overview them all. In fact, it seems that the complexity of the field overcomes the complexity of HER. The aim of this review is to point out some of the latest developments in HER catalysis, current directions and some of the missing links between a single crystal, nanosized supported catalysts and, recently emerging, single atom catalysts for HER.3 of 36 HER at single crystal surfaces and bulk surfacesA crystalline solid can be considered as a series of mutually parallel lattice planes, arranged in a periodic way. Close to the surface, the spatial arrangement of the lattice planes, their crystallographic structure, as well as the dynamics of the constituent atoms may differ from the corresponding features in the bulk [1]. Most clean metals show the tendency to minimize their surface energy. One of the mechanisms is relaxation, the shift of one or more lattice planes located near to the surface, usually perpendicularly to the surface, so that the interlayer distance changes compared to the bulk lattice. The other one is reconstruction -change in equilibrium positions and bonding of surface atoms so that the projection of bulk unit cell to the given surface does not correspond to the surface unit cell. Different crystallographic planes (with different Miller indices) of the same metal exhibit unequal surface densities (number of atoms per surface area), and therefore undergo surface relaxation/reconstruction to different extents [2]. For example, Pt(100) has lower surface density compared to densely packed Pt(111) and therefore has a stronger tendency to relax/reconstruct. Since the main driving force for the mentioned surface modifications is the low coordination number (non-saturation) of surface atoms, it is obvious that atom/molecule adsorption on clean metal surfaces can have a significant effect on its surface structure, inducing relaxation/reconstruction changes. This is of huge importance for HER, as it involves adsorbed atomic hydrogen (Hads) as an intermediate. Additionally, in an electrochemical system, the electrode will be modified by adsorption of "spectator" species (ions/molecules from the electrolyte), so HER will not be taking place on clean metal surfaces, but rather on modified ones. Obviously, there is a complex dynamic interplay between the catalyst surface, reactants, intermediates, and electrolyte.According to the Sabatier principle, the interaction of the reaction reactants/intermediates with the catalyst has to be optimal in strength. If it is too weak, the reactants will not bind to the catalyst and the reaction will not be able to take place. In...

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A rhodium/silicon co-electrocatalyst design concept to surpass platinum hydrogen evolution activity at high overpotentials

Cited by 287 publications

References 25 publications

Vertically Aligned NiCo₂S₄ Nanosheets Deposited on N‐Doped Graphene for Bifunctional and Durable Electrode of Overall Water Splitting

Vertically Aligned NiCo₂S₄ Nanosheets Deposited on N‐Doped Graphene for Bifunctional and Durable Electrode of Overall Water Splitting

In‐situ Tailoring Cobalt Nickel Molybdenum Oxide Components for Overall Water‐Splitting at High Current Densities

Hydrogen Evolution Reaction - From Single Crystal to Single Atom Catalysts

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A rhodium/silicon co-electrocatalyst design concept to surpass platinum hydrogen evolution activity at high overpotentials

Cited by 287 publications

References 25 publications

Vertically Aligned NiCo2S4 Nanosheets Deposited on N‐Doped Graphene for Bifunctional and Durable Electrode of Overall Water Splitting

Vertically Aligned NiCo2S4 Nanosheets Deposited on N‐Doped Graphene for Bifunctional and Durable Electrode of Overall Water Splitting

In‐situ Tailoring Cobalt Nickel Molybdenum Oxide Components for Overall Water‐Splitting at High Current Densities

Hydrogen Evolution Reaction - From Single Crystal to Single Atom Catalysts

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Vertically Aligned NiCo₂S₄ Nanosheets Deposited on N‐Doped Graphene for Bifunctional and Durable Electrode of Overall Water Splitting

Vertically Aligned NiCo₂S₄ Nanosheets Deposited on N‐Doped Graphene for Bifunctional and Durable Electrode of Overall Water Splitting