Investigating Catalyst–Support Interactions To Improve the Hydrogen Evolution Reaction Activity of Thiomolybdate [Mo3S13]2– Nanoclusters

Hellstern, Thomas R.; Kibsgaard, Jakob; Tsai, Charlie; Palm, David W.; King, Laurie A.; Abild‐Pedersen, Frank; Jaramillo, Thomas F.

doi:10.1021/acscatal.7b02133

Cited by 80 publications

(64 citation statements)

References 53 publications

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“…The Si/Ti/Au substrate, particularly in acidic conditions, seems to govern the experimental Tafel slopes obtained after MoS x modification across the 0–10 pH range: supporting working electrodes of different nature and morphology yielded analogous results in previous HER experiments.…”

Section: Resultssupporting

confidence: 70%

Benchmarking the Activity, Stability, and Inherent Electrochemistry of Amorphous Molybdenum Sulfide for Hydrogen Production

Escalera‐López

Lou

Rees

2019

Advanced Energy Materials

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can be efficiently produced on demand and in a decentralized manner with (photo) electrochemical methods via the hydrogen evolution reaction (HER). [1][2][3][4] Despite of being the best performing HER catalysts, [5,6] noble metals such as Pt, Ir, and Pd are scarce and consequently hamper the viability of water electrolysis technologies. Hence earth-abundant materials, and notably transition metal dichalcogenides (TMDs) such as molybdenum disulfide (MoS 2 ), have been extensively investigated as HER electrocatalysts. [7][8][9][10][11] The edge sites-driven hydrogen electroadsorption properties of TMDs [12,13] have prompted the fabrication of amorphous molybdenum sulfide materials (MoS x ) to minimize exposure of the electrocatalytically inert MoS 2 basal planes [14] for multiple applications. [15][16][17][18][19] A simple, yet scalable method to fabricate MoS x has been reported by substrate-insensitive electrodeposition from a [MoS 4 ] 2− precursor, [20,21] and critical properties in MoS x materials such as film thickness, [22] morphology, [23][24][25][26] Mo:S stoichiometry, [27] as well as incorporation of dopants [28][29][30] or nanocomposite formation, [31][32][33][34][35] have been easily tuned by experimental parameters.For long-term electrocatalytic applications, however, HER activity and stability of TMDs are paramount. In crystalline MoS 2 , basal plane activation, [36][37][38][39][40][41][42][43] edge site exposure, [44][45][46][47][48][49][50][51][52][53] and metal doping/incorporation/intercalation [54][55][56][57][58][59][60][61][62][63][64][65][66] are the most employed strategies.In contrast, the [Mo 3 S 13 ] 2− cluster-based polymeric structure of electrodeposited MoS x[67] requires alternative approaches to maximize activity. In addition, the detailed HER mechanism as well as the true catalytically active sites are still under debate. Whilst pioneering studies on ambient pressure X-ray photoelectron spectroscopy (XPS) indicated the MoS 2 edge-like sites formed after MoS 3 phase transformation under in operando conditions responsible for the HER performance, [68] in situ X-ray absorption spectroscopy experiments suggested terminal S 2 2− ligands (S 2 2− terminal ) to be the proton acceptor sites, [69] and more recently in situ Raman spectroscopy indicated these to be the electrochemically cleaved bridging S 2 2− ligands (S 2 2− bridging ). [70] Another study claimed that unsaturated Mo centers formed after cathodic dissolution of S 2 2− terminal to be the true HER Anodically electrodeposited amorphous molybdenum sulfide (AE-MoS x ) has attracted significant attention as a non-noble metal electrocatalyst for its high activity toward the hydrogen evolution reaction (HER). The [Mo 3 S 13 ] 2− polymerbased structure confers a high density of exposed sulfur moieties, widely regarded as the HER active sites. However, their intrinsic complexity conceals full understanding of their exact role in HER catalysis, hampering their full potential for water splitting applications. In this report, a unifying app...

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Section: Resultssupporting

confidence: 70%

Benchmarking the Activity, Stability, and Inherent Electrochemistry of Amorphous Molybdenum Sulfide for Hydrogen Production

Escalera‐López

Lou

Rees

2019

Advanced Energy Materials

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“…Therefore, research into and development of alternative electrocatalysts based on earth-abundant materials has attracted considerable interest [8][9][10]. Heretofore, a broad range of earth-abundant electrocatalysts have been developed for either HER (e.g., molybdenum-based sulfides [11,12], carbides [13,14], and phosphides [15]) or OER (e.g., transition metal-based oxides [16,17], layered double hydroxides [18,19], and sulfides [20,21]); some of them even performed comparably to noble metals. However, it is still difficult to pair HER and OER electrode reactions together in an integrated electrolyzer due to the mismatch of pH ranges in which these catalysts remain stable and highly active.…”

Section: Introductionmentioning

confidence: 99%

Elaborately assembled core-shell structured metal sulfides as a bifunctional catalyst for highly efficient electrochemical overall water splitting

et al. 2018

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Low efficiency, short lifetimes, and limited kinds of catalysts are still three fundamental shortcomings that have plagued electrochemical water splitting. Herein, we rationally synthesized a cost-effective Co 3 S 4 @MoS 2 hetero-structured catalyst that has proven to be a highly active and stable bifunctional catalyst for both hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) in an alkaline environment. The heterostructure was obtained via a first hydrothermal approach to obtain hollow Co 3 S 4 nanoboxes based on the ionic exchange reaction between Fe(CN) 6 3of Co-Fe Prussian blue analogue (PBA) and S 2at 120 ºC, and the subsequent in-situ growth of MoS 2 nanosheets on the surface of Co 3 S 4 nanoboxes at an elevated temperature of 200 ºC. The synergistic effects between the active and stable HER catalyst of MoS 2 and the efficient OER catalyst of Co 3 S 4 , as well as the morphological superiority of hollow and core-shell structures, endow Co 3 S 4 @MoS 2 with remarkable electrocatalytic performance and robust durability toward overall water splitting. As a result, the designed non-noble electrocatalyst of Co 3 S 4 @MoS 2 exhibits a low overpotential of 280 mV for OER and 136 mV for HER at a current density of 10 mA•cm-2 in an alkaline solution. Meanwhile, a low cell voltage of 1.58 V is achieved by using the heterostructure as both anode and cathode catalysts. This work paves the way to the design and construction of other prominent electrocatalysts for overall water splitting.

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“…In this regard, it is of great interest to explore nanostructured non‐noble metal catalysts by virtue of their exceptionally high stability and electrocatalytic activity for both the HER and the oxygen evolution reaction in basic solutions. Whereas earth‐abundant monometallic transition‐metal catalysts, such as Fe, Co, Ni, Ti, W, Mo, and Cu, usually show much lower catalytic activity than traditional carbon‐supported Pt (Pt/C) nanoparticles because of either too strong or too weak HBE, initial strides have been made to improve their HER activities by developing their alloys (such as Ni‐Mo, Cu‐Ti) and compounds (such as chalcogenides, nitrides, carbides, and phosphides). These catalysts are generally synthesized as powders or colloids with various low‐dimensional nanostructures and immobilized on planar current collectors by making use of insulative polymer binders to maintain electrical contact for electron transfer in the practical alkaline electrolysis .…”

Section: Introductionmentioning

confidence: 99%

Nonprecious Intermetallic Al₇Cu₄Ni Nanocrystals Seamlessly Integrated in Freestanding Bimodal Nanoporous Copper for Efficient Hydrogen Evolution Catalysis

Sun

Wen

Han

et al. 2018

Adv Funct Materials

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Tremendous demands for renewable hydrogen generated from water splitting have stimulated intensive research on developing earth-abundant, non-noble, and versatile metal catalysts toward the hydrogen evolution reactions (HER). Here, self-supported Cu-Ni-Al hybrid electrodes that are composed of electroactive Al 7 Cu 4 Ni@Cu 4 Ni core/shell nanocrystals seamlessly integrated in selfsupported 3D bimodal nanoporous Cu skeleton (Bi-NP Cu/Al 7 Cu 4 Ni@Cu 4 Ni) as robust HER electrocatalysts in alkaline electrolyte are reported. As a result of the proper architecture, in which the Bi-NP Cu skeleton not only facilitates both electron and electrolyte transports but also provides high specific surface areas to fully use high electrocatalytic activity of Al 7 Cu 4 Ni@Cu 4 Ni core/shell nanocrystals, the Bi-NP Cu/Al 7 Cu 4 Ni@Cu 4 Ni hybrid catalysts exhibit a low onset overpotential of 60 mV and a small Tafel slope of 110 mV dec −1 , enabling the catalytic current density of 10 mA cm −2 at a low overpotential of 139 mV. The highly stable electrochemical performance makes them promising candidates as cathode catalysts in alkaline-based devices.

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Investigating Catalyst–Support Interactions To Improve the Hydrogen Evolution Reaction Activity of Thiomolybdate [Mo₃S₁₃]^2– Nanoclusters

Cited by 80 publications

References 53 publications

Benchmarking the Activity, Stability, and Inherent Electrochemistry of Amorphous Molybdenum Sulfide for Hydrogen Production

Benchmarking the Activity, Stability, and Inherent Electrochemistry of Amorphous Molybdenum Sulfide for Hydrogen Production

Elaborately assembled core-shell structured metal sulfides as a bifunctional catalyst for highly efficient electrochemical overall water splitting

Nonprecious Intermetallic Al₇Cu₄Ni Nanocrystals Seamlessly Integrated in Freestanding Bimodal Nanoporous Copper for Efficient Hydrogen Evolution Catalysis

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Investigating Catalyst–Support Interactions To Improve the Hydrogen Evolution Reaction Activity of Thiomolybdate [Mo3S13]2– Nanoclusters

Cited by 80 publications

References 53 publications

Benchmarking the Activity, Stability, and Inherent Electrochemistry of Amorphous Molybdenum Sulfide for Hydrogen Production

Benchmarking the Activity, Stability, and Inherent Electrochemistry of Amorphous Molybdenum Sulfide for Hydrogen Production

Elaborately assembled core-shell structured metal sulfides as a bifunctional catalyst for highly efficient electrochemical overall water splitting

Nonprecious Intermetallic Al7Cu4Ni Nanocrystals Seamlessly Integrated in Freestanding Bimodal Nanoporous Copper for Efficient Hydrogen Evolution Catalysis

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Product

Resources

About

Investigating Catalyst–Support Interactions To Improve the Hydrogen Evolution Reaction Activity of Thiomolybdate [Mo₃S₁₃]^2– Nanoclusters

Nonprecious Intermetallic Al₇Cu₄Ni Nanocrystals Seamlessly Integrated in Freestanding Bimodal Nanoporous Copper for Efficient Hydrogen Evolution Catalysis