Boosting Electrocatalytic Hydrogen Evolution Activity with a NiPt3

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Boosting Electrocatalytic Hydrogen Evolution Activity with a NiPt3@NiS Hetero-Nanostructure Evolved from a Molecular Nickel-Platinum Precursor Chakadola Panda, Prashanth W. Menezes, Shenglai Yao, Johannes Schmidt, Carsten Walter, Jan Niklas Hausmann, and Matthias Driess J. Am. Chem. Soc., Just Accepted Manuscript • DOI: 10.1021/jacs.9b06530 • Publication Date (Web): 14 Aug 2019 Downloaded from pubs.acs.org on August 14, 2019

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Boosting Electrocatalytic Hydrogen Evolution Activity with a NiPt3@NiS Hetero-Nanostructure Evolved from a Molecular NickelPlatinum Precursor Chakadola Panda,†# Prashanth W. Menezes,*†# Shenglai Yao,† Johannes Schmidt,‡ Carsten Walter,† Jan Niklas Hausmann,† and Matthias Driess*† †Department

of Chemistry: Metalorganics and Inorganic Materials, Technische Universität Berlin, Straße des 17 Juni 135, Sekr. C2, 10623 Berlin, Germany ‡ Department of Chemistry, Functional Materials, Technische Universität Berlin, Hardenbergstr. 40, 10623 Berlin, Germany Supporting Information Placeholder ABSTRACT: A facile synthetic route to NiPt3@NiS hetero-

nanostructures is reported, starting from a subsulfido bridged heterobimetallic nickel-platinum molecular precursor. Notably, the NiPt3@NiS on nickel foam displayed merely an overpotential of 12 mV at -10 mAcm-2, which is substantially lower than Pt or NiS, synthesized through a similar approach and represents the most active hydrogen evolution reaction (HER) electrocatalysts yet reported in alkaline solutions. NiPt3@NiS electrodes demonstrated an unceasing HER stability over eight days, which is well over those reported for Pt-based catalysts signifying capability of scaled hydrogen production. Figure 1. Synthesis of NiPt3@NiS hetero-nanostructure from 1. Sustainable large-scale electrochemical production of hydrogen from water is a promising approach to devise carbon-neutral energy technologies.1 Platinum is best known for its ability to efficiently catalyze the hydrogen evolution reaction (HER) owing to its optimum d-band center with ideal adsorption/desorption energies for reactive intermediates.2 Despite exorbitant cost and scarcity; platinum has been extensively used in most of the commercial electrolyzers as cathode material to deliver efficient HER. In the meantime, a great deal of research efforts have been devoted to design and develop alternative electrocatalysts based on earthabundant transition metals,3-5 and among them, metal phosphides68, chalcogenides,9-11 metal oxides12, and non-noble metal alloys13 have attracted particular attention displaying promising results. However, when the cost and efficiency are taken into consideration, a significant gap exists between the state of the art Pt- and the nonnoble based catalytic systems. Therefore, precedence is given to improve the activity and stability of Pt-based catalysts by doping/alloying with various non-noble metals.14-21 Besides, to overcome the limitations of Pt for slow HER kinetics,15,22 various promoters have been developed to enhance net catalytic activity as well as the stability of the system. To realize the bifunctional effect, the edges of Ni(OH)2 clusters was first used as a promoter for the dissociation of water (OH…H+) to generate a vast amount of hydrogen intermediates followed by adsorption (Had) and recombination on Pt(111) surface to accelerate alkaline HER.15 Based on this, a design synthetic strategy was applied by modifying the surface of Ni(OH)2 nanosheets with subsequent immobilization and growth of ultrathin Pt nanowires, and this hybrid material exhibited exceptional catalytic activity towards HER in alkaline solution.20 Meanwhile, surface engineered PtNi nanoparticles enriched with NiO

and Pt on Ni3N was prepared, which in alkaline media lead to insitu generated Ni(OH)2/Pt interfaces, demonstrating enhanced capability for HER.21,23 Along this line, the concept was further extended recently to sulfides where composition-segregated PtxNiy nanowires were synthesized, and under simple sulfuration, PtxNi/NiS heterostructures were formed.19 This high interactive interfaces between PtxNi and NiS displayed superior HER activity due to improved kinetics. In this respect, novel synthetic approaches for designing multicomponent electrocatalysts with tailored interfaces and electronic structures to achieve maximum catalytic output both in terms of activity as well as kinetics is of utmost interest.24 By taking advantage of the low-temperature molecular singlesource precursor approach, 25 we have successfully utilized metal complexes to design multi-functional nanostructured materials and demonstrated their prominence in OER, HER and overall water splitting.26,27 Here we present the unexpectedly facile formation of a NiPt3@NiS hetero-nanostructure based on nickel-platinum alloy (NiPt3) embedded homogeneously in an amorphous matrix of nicNiS derived from the subsulfido-bridged heterobimetallic nickel-platinum precursor 1.28 The tailored NiPt3@NiS is unique and offers access to higher interactive interfaces between Pt3Ni and NiS and, to the best of our knowledge, represents the most efficient alkaline HER catalyst reported to-date outperforming even pristine Pt and NiS electrodes synthesized via a similar approach. We further demonstrate how kinetic synergy between catalytically active NiPt3 and water dissociation promoter NiS in NiPt3@NiS can maximize the rate of HER with long-lasting durability, which is of great significance for commercial water-alkaline and chlorinealkaline metal electrolyzers.

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NiPt3@NiS was synthesized through hot injection of 1 in oleylamine at 200 °C which caused liberation of the weakly coordinated ligands at Ni and Pt (Figure 1; Figure S1 and S2, Supporting Information) and concomitant nucleation of NiPt3 alloy along with NiS formation. The powder X-ray diffraction (PXRD) pattern revealed broad reflexes (Figure S3), due to the extremely small particle size and the 2θ values slightly deviated from that of elemental nickel and platinum. This resulted from the alloying of the respective metals in the reductive decomposition of the precursor. The structural parameters attained from Rietveld refinement, and subsequent application of Vegard’s rule further confirmed the extent of alloying corresponding to the composition of 25% Ni and 75% Pt (NiPt3; Figure S3, Table S1, and S2). The high-resolution transmission electron microscopy (HR-TEM) of the as-prepared NiPt3@NiS particles displayed extremely small (~2 nm) spherical homogeneously distributed crystalline particles embedded in a homogeneous amorphous support/matrix (Figure 2a-d and S4). The lattice fringes with an interplanar spacing of 0.22 nm correspond to the (111) plane, and the selected area electron diffraction (SAED) rings of the crystalline particles indicated the formation of NiPt3 while the amorphous phase contained NiS. Nature and composition of the amorphous layer was analyzed by scanning electron microscopy (SEM) that showed agglomerated particles, and energy dispersive X-ray (EDX) mapping exhibited the homogeneous distribution of the respective elements Ni, Pt and S with ratios of 1.3:1.0:1.0 (Figures 2e-h and S5, Table S3). Further, the bulk material composition was proven by inductively coupled plasma atomic emission spectroscopy (ICP-AES) that nearly matched with the EDX data (40% Ni, 30% Pt and 30% S; Figure S5, Table S3). Therefore, we can deduce that NiPt3 remained crystalline deeply embedded in the amorphous NiS phase forming NiPt3@NiS. The X-ray photoelectron spectroscopy (XPS) was also carried out to support the elemental composition and trace the chemical state of the respective elements (Ni, Pt, and S) in the as-prepared NiPt3@NiS and the detailed description is provided in Figure S6. Similarly, elemental Pt and NiS materials were prepared and thoroughly characterized (Figure S7-S16). The as-synthesized NiPt3@NiS was deposited electrophoretically on 3D porous conductive nickel foam (NF) substrate and the HER activities were evaluated in 1 M KOH solution. On application of reductive potential at a rate of 1 mVs-1, strikingly, NiPt3@NiS/NF delivered overpotentials nearly 12 and

73 mV at the HER current densities of -10 and -100 mAcm-2, respectively (Figure 3a-b), which, to the best of our knowledge, is one of the lowest values reported for any noble and non-noblebased materials (Table S4).15,18,19,21,29 In contrast, Pt/NF (100% Pt) delivered such current densities only at 22 and 107 mV overpotentials, respectively, which is 10 and 34 mV higher than that of NiPt3@NiS/NF. This is a clear indication that both amorphous NiS and crystalline NiPt3 alloy in NiPt3@NiS play a crucial role in accelerating HER activity. As anticipated, NiS/NF was moderately active towards HER that requires overpotentials of 107 and 229 mV to furnish current densities of 10 and 100 mAcm2, respectively, while bare NF was almost inert within the provided potential window. Tafel plots were drawn to compare reaction kinetics and understand the rate-determining step (RDS) and hence, the HER reaction mechanism. A slope of 24 mVdec-1 for NiPt3@NiS/NF that suggests the participation of Heyrovsky (Hads + H+ +e- → H2) and/or Tafel (Hads + Hads → H2) steps in the RDS.30 Moreover, a low Tafel slope of NiPt3@NiS/NF compared to Pt/NF (31 mVdec-1), and NiS/NF (71 mVdec-1) represents better kinetics (Figure 3c). The chronoamperometric (CA) test on NiPt3@NiS/NF electrodes was conducted by applying an HER overpotential at 12 and 75 mV (Figure 3d, inset, Figure S17) that exhibited unceasing stability over eight days and 24 h rendering its high robustness (~100% Faradaic efficiency). However, the Pt/NF electrode at an overpotential of 22 mV displayed a significant drop in current density (~40%) within two days (Figure 3d). On the other hand, the NiS/NF maintained the current density at -10 mAcm-2 over two days with a higher overpotential (107 mV), The electrochemical active surface area (ECSA) and the impedance spectroscopy (EIS) of all the three presented catalysts were performed to correlate with the aforementioned superior activity of NiPt3@NiS/NF over Pt/NF and NiS/NF. Cycling within a non-faradic region at various scan rates, allowed us to attain a double-layer capacitance (Cdl), which is 71, 43 and 1.7 mFcm-2 for NiPt3@NiS/NF over Pt/NF and NiS/NF, respectively (Figure S18S19, Figure 3e). Consequently, the estimated ECSA value from Cdl was about 42 cm2, which was almost twice larger and 44 times (~1 cm2) larger to Pt/NF and NiS/NF, respectively. Besides, the EIS confirmed lower charge transfer resistance of NiPt3@NiS/NF compared to Pt/NF as well as NiS/NF demonstrating improved electron transport property (Figure 3f).

Figure 2. (a) TEM images of the as-prepared NiPt3@NiS showing homogeneously distributed tiny spherical nanoparticles of diameter ~2 nm; (b) SAED patterns of NiPt3@NiS matching clearly with reported NiPt3 (green box); (c) HR-TEM image of NiPt3@NiS that distinguishes between the crystalline NiPt3 phase (green) and amorphous NiS (violet) phase; d) SAED patterns obtained for NiPt3@NiS indicating amorphous nature (violet box); (e-h) SEM image of NiPt3@NiS along with EDX elemental mapping for Ni (blue), Pt (yellow) and S (red).

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We further electrophoretically deposited NiPt3@NiS, Pt and NiS on a relatively inert fluorine-doped tin oxide (FTO) substrate and similarly examined their HER activity as that on NF. The NiPt3@NiS/FTO delivered an overpotential of only 40 mV at a current density of -10 mAcm-2 which is 25 mV lower compared to Pt/FTO and NiS/FTO displayed limited activity (Figure S20a). Additionally, the Tafel slope of NiPt3@NiS/FTO was 39 mVdec-1, while for Pt/FTO and NiS/FTO, a slope of 45 and 123 mVdec-1 resulted confirming favorable kinetics of NiPt3@NiS/FTO (Figure S20b). The boost in catalytic activity of NiPt3@NiS for HER encouraged us to gather an in-depth understanding of the system as well as to uncover the active structures (multi-component) in comparison to Pt and NiS using microscopy and spectroscopy. The HRTEM of the NiPt3@NiS after HER CA revealed almost no change in the crystalline NiPt3 phase thereby retaining all the crystal lattices of the as-synthesized NiPt3 but the amorphous NiS phase was affected considerably forming Ni(OH)x because of sulfur leaching and structural conversion (defects or disorder) owing to hydroxides ions of the electrolyte (Figure S21).21 This was further supported by the EDX spectrum of the as-synthesized NiPt3@NiS (Figure S5) and used NiPt3@NiS (Figure S22). The extent of leaching of sulfur and nickel during catalysis, as quantified by ICP-AES of the used electrolyte, was ~40.3 and 2.03%, respectively, suggesting partial hydroxylation (Ni(OH)x) of NiS. The XPS results of Ni 2p and Pt 4f after HER CA did not reveal any severe changes in the oxidation of Ni (Ni0 and NiII) and Pt (Pt0 and PtII). However, the slightly higher oxidation of S was evident from S 2p, compared to the as-synthesized NiPt3@NiS (Figure S23).19 Moreover, the O1s peak at 531.6 eV clearly indicated the presence of Ni(OH)x that indeed implies that the active structure of HER comprises of NiPt3@NiS/Ni(OH)x.6 The results established here are strikingly in close connections with the Ni(OH)2-Pt interfaces and surface engineered PtNi-O(H) nanostructure, where Ni(OH)2 acts as a promoter for water dissociation and Pt, as an active site for H2 evolution.15 In fact, the density functional theory (DFT) calculations performed on the recently reported PtxNi/NiS also emphasized the crucial role of NiS as an active promoter for water dissociation.19 Therefore, the accelerated HER activity and kinetics of the presented NiPt3@NiS can be associated to dual promotion effect, assisted by NiS and

Ni(OH)x in the first step of water dissociation and followed by immediate adsorption of H+ to form the surface adsorbed intermediates (Had) on the NiPt3 surfaces and recombination of two Had to the evolution of H2.15 Conversely, the metallic Pt tested after HER showed good structural or morphological stability apart from the surface oxidation while the NiS lost most of its crystallinity as well as sulfur from the structure to yield Ni(OH)x (Figure S24-S29). This again underlines the advantage of tailored multiple (NiPt3@NiS) hetero-nanostructures for HER instead of using the single (Pt or NiS) components. In summary, we have successfully applied the single-source molecular precursor approach for the interface engineering of ultrasmall crystalline nickel-platinum alloy and amorphous nickel sulfide hetero-nanostructures for boosting electrochemical alkaline HER. To the best of our knowledge, the attained overpotential of 12 mV at a current density of 10 mAcm-2, is one of the lowest in comparison to any reported noble and non-noble metal-based catalysts reported to date with outstanding durability over eight days. This study provides a ‘bifunctional pathway’ from the designed molecular precursor to the high density of atomically controlled active sites and efficient promoters for water dissociation to accelerate H2 evolution.

ASSOCIATED CONTENT Supporting Information The Supporting Information is available free of charge on ACS Publications website at DOI: Detailed synthetic procedure, characterization, electrocatalysis and post-electrocatalytic characterizations

AUTHOR INFORMATION Corresponding Author *[email protected] *[email protected]

ORCID Prashanth W. Menezes: 0000-0002-0665-7690 Matthias Driess: 0000-0002-9873-4103

Author Contributions #These

authors (C. P and P. W. M.) contributed equally.

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Figure 3. (a) LSV polarization curves of HER at a scan rate of 1 mVs-1; (b) bar diagram representing the overpotentials at 10 mAcm-2; (c) Tafel plots; (d) HER CA responses (inset shows over eight days of CA for NiPt3@NiS/NF);(e) the double-layer capacitance and (f) Nyquist plots (inset: enlarged view) of NiPt3@NiS/NF, Pt/NF, NiS/NF in 1 M KOH solution.

Notes The authors declare no competing financial interests.

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ACKNOWLEDGMENTS Financial support by the Deutsche Forschungsgemeinschaft (UniSysCat, EXC 2008/1–390540038) is gratefully acknowledged. The authors are also indebted to Mr. Christoph Fahrenson (TU Berlin) for SEM.

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Table of Content Boosting Electrocatalytic Hydrogen Evolution Activity with a NiPt3@NiS Hetero-nanostructure Evolved from a Molecular Nickel-Platinum Precursor Chakadola Panda, Prashanth W. Menezes, Shenglai Yao, Johannes Schmidt, Carsten Walter, Jan Niklas Hausmann, and Matthias Driess

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