Enhanced the Hydrogen Evolution Performance by Ruthenium

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Enhanced the Hydrogen Evolution Performance by Ru Nanoparticles Doped into Cobalt Phosphide Nanocages Chong-Dian Si, Zexing Wu, Jing Wang, Zhi-Hua Lu, Xiufeng Xu, and Ji-Sen Li ACS Sustainable Chem. Eng., Just Accepted Manuscript • DOI: 10.1021/ acssuschemeng.9b00817 • Publication Date (Web): 10 May 2019 Downloaded from http://pubs.acs.org on May 10, 2019

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ACS Sustainable Chemistry & Engineering

Enhanced the Hydrogen Evolution Performance by Ru Nanoparticles Doped into Cobalt Phosphide Nanocages Chong-Dian Si,† Ze-Xing Wu,†† Jing Wang,† Zhi-Hua Lu,† Xiu-Feng Xu,††† and Ji-Sen Li†,*

†

Key Laboratory of Inorganic Chemistry in Universities of Shandong, Department of Chemistry

and Chemical Engineering, Jining University, Qufu, 1# Xingtan Road, Shandong 273155, P. R. China ††

State Key Laboratory Base of Eco-chemical Engineering, College of Chemistry and Molecular

Engineering, Qingdao University of Science & Technology, 53# Zhengzhou Road, Qingdao 266042, P.R. China †††

School of Chemistry and Chemical Engineering, Institute of Applied Catalysis, Yantai

University, Yantai, 30# Qingquan Road, Shandong 264005, P.R. China E-mail: [email protected]

1 ACS Paragon Plus Environment

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ABSTRACT: The development of highly active and robust Pt-free catalysts is of great significance for electrocatalytic hydrogen production. Herein, we illustrate the design of Rudoped cobalt phosphide nanocages as a high-efficiency electrocatalyst toward the hydrogen evolution reaction (HER) in acid condition. Remarkably, the composite shows excellent HER behavior with a low onset potential of 41 mV, a small Tafel slope of 54.7 mV dec-1 as well as good durability for 10 h. The enhanced catalytic activity for the HER could be assigned to the synergistic contribution of unique composition and structure of the hybrid catalyst. Consequently, this work offers a promising replacement for Pt-based nanomaterials for hydrogen generation from water-splitting.

KEYWORDS: Ru-doping, cobalt phosphide, nanocages, hydrogen evolution reaction, metalorganic frameworks INTRODUCTION Hydrogen is a clean, sustainable, and viable fuel carrier candidate for fossil energy. Currently, electrolysis of water has been regarded as an effective solution to generate pure hydrogen.[1-4] To achieve large-scale hydrogen production, a highly efficient and stable electrocatalyst that can trigger proton reduction with lower overpotential plays a crucial role in hydrogen evolution reaction (HER).[5-13] As is well known, Pt-based materials are the most efficient electrocatalysts toward HER. Nevertheless, their wide applications are greatly hampered by the high cost and natural scarcity.[14-20] Therefore, it is of great significance to exploit highly efficient and inexpensive non-Pt-based catalysts for HER. Recently, transition metal phosphide (TMP)-based hybrids have attracted considerable interest because of their low cost and excellent HER performance.[21-33] Unfortunately, the Tafel slopes and overpotentials of single TMP-based


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materials are still higher than those of Pt-based catalysts due to their low electrical conductivity. In addition, the surface oxidation and aggregation of TMP nanoparticles during long-term preparation usually lead to the degradation of electrocatalytic activity. To improve the electrocatalytic efficiency, TMP-based catalysts coupled with carbon materials have been considered as a promising strategy for design of high-efficiency electrocatalysts for HER.[8, 28] Benefiting from their fascinating properties, metal-organic frameworks (MOFs)-derived functional composites have been extensively applied in energy storage and conversion devices.[34, 35]

During heat treatment, MOFs could be transformed into porous carbons and metal

phosphides,[23, 36] metal nitrides[37] and so on.[38, 39] More importantly, these small-sized metal nanoparticles are usually embedded in porous carbons, which could effectively prevent nanoparticles from oxidation and agglomeration and enhance the HER activity. As a cheap substitution of Pt-group metal, ruthenium (Ru) possesses Pt-like Ru-H binding energy.[40,

41]

However, to the best of our knowledge, only a few of Ru-based nanohybrids have been regarded as HER electrocatalysts to date.[42-49] Inspired by this, we envision that the introduction of Ru into TMPs-based catalysts using MOFs as precursor could be a powerful strategy to significantly promote the catalytic activities of the resulting products toward HER. Herein, we present that the ingenious construction of Ru-doped cobalt phosphide nanoparticles@N-doped carbon nanocages composite (Ru/CoxP@NC) by pyrolysis and subsequent phosphidation of Ru-doped Co3[Co(CN)6]2 (Ru-Co3[Co(CN)6]2). Impressively, the Co and Ru atoms of Ru-Co3[Co(CN)6]2 could convert into Ru/CoxP nanoparticles, which are embedded into NC nanocages stemming from other CN- linkers.[50-53] Owing to the merit of unique morphology and constituents, the resulting Ru/CoxP@NC hybrid exhibits advanced



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electrocatalytic ability toward the HER, which is in comparison with some other HER catalysts reported by far. RESULTS AND DISCUSSION

Scheme 1. Illustration of the formation process of Ru/CoxP@NC. The preparation of Ru/CoxP@NC is schematically demonstrated in Scheme 1. According to the previously reported literature,[44] Co3[Co(CN)6]2 was synthesized by a coprecipitation approach. In the first step, the Ru3+ was successfully doped into the framework of Co3[Co(CN)6]2 via a facile ion-exchange process (step I). In step II, the obtained Ru-Co3[Co(CN)6]2 was transformed into Ru-doped Co3O4@NC (Ru-Co3O4@NC) after annealing at 350 oC under an air atmosphere. Lastly, the Ru/CoxP@NC hybrid consisting of a mixture of Co2P and CoP encapsulated in NC nanocages was prepared after phosphidation.


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Figure 1. (a) SEM, (b, c) TEM images, and (d) PXRD of Co3[Co(CN)6]2. Scanning electron microscopy (SEM) image of Co3[Co(CN)6]2 in Figure S1a presents that the resulting truncated nanocubes with smooth surface are quite homogeneous, which has an average size of approximate 200 nm. Transmission electron microscopy (TEM) images further confirm the morphology of truncated nanocubes (Figures S1b, c). As depicted in Figure S1d, the powder X-ray diffraction (PXRD) pattern evidences the fabrication of phase-pure Co3[Co(CN)6]2.[44, 54] After adding the RuCl3 solution, the Ru3+ can partially replace Co3+ of Co3[Co(CN)6]2, leading to the formation of Ru-Co3[Co(CN)6]2, which are examined by SEM, TEM and PXRD (Figure 1), respectively. Notably, these results are in agreement with those of Co3[Co(CN)6]2, which prove that the introduction of Ru3+ does not alter the crystalline structure and morphology of Co3[Co(CN)6]2.[44] Subsequently, the porous Ru-Co3O4@NC nanocages with rougher surface were obtained during the heat treatment, but the corresponding particle size slightly decreases (Figures S2a-c). The cubic Co3O4 nanocrystal features are also presented in the PXRD pattern (Figure S2d).[51]



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Figure 2. (a) SEM, (b) TEM, (c) HRTEM, (d) STEM and corresponding elemental mappings of Ru/CoxP@NC. Scale bar: 100 nm. After phosphidation, the Ru-Co3O4@NC was converted into Ru/CoxP@NC and the nanocage structure is perfectly preserved (Figures 2a, b). This sufficiently suggests that the Co3[Co(CN)6]2 nanocubes can be utilized as ideal precursor for the synthesis of Ru/CoxP@NC nanocages, which are composed of numerous pores with rich smaller nanoparticles. Importantly, the distinctive architecture is advantageous to limit the aggregation of the nanoparticles.[23,

44]

The high-

resolution TEM (HRTEM) image (Figure 2c) displays that the interplanar distances of 0.285 and 0.247 nm are attributed to the (120) lattice plane of Co2P and (111) lattice plane of CoP, whereas that of 0.234 nm corresponds to (100) plane of Ru, respectively. Moreover, it is found that these nanoparticles are decorated by a thin carbon layer, which is measured to be approximately 1.2 nm. The scanning transmission electron microscopy (STEM) image and energy-dispersive X-ray spectroscopy (EDX) elemental mappings images in Figure 2d confirm the uniform distribution of C, N, Ru, Co, and P in Ru/CoxP@NC. At the same time, the Ru content is estimated to be about 3.31wt% from EDX measurement (Figure S3). In consideration of the porous structure, the Brunauer-Emmett-Teller (BET) surface area of Ru/CoxP@NC is 12.7 m2 g-1 (Figure S4), which is slightly lower than that of CoxP@NC (26.8 m2 g-1). In this regard, this may be related to the dopant of Ru nanoparticles, which could result in blocking partial interior space of the nanocages,


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thus reducing specific surface area. Such a porous nanocage structure is expected to protect nanoparticles from corrosion and provide sufficient contact area, consequently boosting the electrocatalytic performance and stability for the HER.[29] Additionally, the content of Co and Ru are measured to be approximate 18.3 and 3.42 wt.%, respectively, which are obtained by inductively coupled plasma-optical emission spectrometry (ICP-OES).

Figure 3. (a) PXRD pattern and high-resolution XPS spectra of (b) C 1s, (c) N 1s, (d) Co 2p, (e) Ru 3p and (f) P 2p for Ru/CoxP@NC. As exhibited in Figure 3a, the PXRD of Ru/CoxP@NC is consistent with orthorhombic Co2P (JCPDS 32-306), orthorhombic CoP (JCPDS 29-497), and hexagonal Ru (JCPDS 65-1863), while the broad peak of carbon at about 23o can be observed, which further verifies the HRTEM observations. The presence of Ru along with C, N, Co, and P elements is further corroborated by X-ray photoelectron spectroscopy (XPS) survey spectra of Ru/CoxP@NC (Figure S5). The high-



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resolution C 1s spectrum (Figure 3b) could be fitted into three peaks at 284.8 eV (C-C/C=C), 286.2 eV (C-N), and 289.2 eV (O-C=O), respectively.[9] The N 1s XPS spectrum shows three individual types of N species (Figure 3c), which belong to graphitic-N (400.5 eV), pyrrolic-N (399.6 eV), and pyridinic-N (398.5 eV).[8] The C 1s and N 1s spectra certify the successful incorporation of N into the carbon nanocages.[30, 43] Especially, the dopant of N could regulate the charge density distribution, further exposing more active sites. As shown in Figure 3d, the peaks of the Co 2p spectrum at 778.6 and 793.5 eV can be identified as Co 2p3/2 and Co 2p1/2, respectively, which are ascribed to CoxP species. Meanwhile, the two doublets centered at 785.9/802.8 eV and 781.4/797.79 eV correspond to the satellite peaks and Co-O bonds, respectively.[28, 55] The Ru 3p XPS peak (Figure 3e) can be fitted into two peaks at 461.8 eV (Ru 3p3/2) and 483.9 eV (Ru 3p1/2), suggesting the presence of Ru0.[42, 43] As expected, the Ru and CoxP nanoparticles as active species would contribute to the excellent HER performance. In view of P 2p spectrum (Figure 3f), the peaks (129.4/130.3 eV) are assigned to P-Co in the Ru/CoxP@NC, while the other peak (133.8 eV) reflects oxidized phosphorus species as a result of surface oxidation of CoxP.[22] Noteworthily, the binding energy (778.6 eV) of Co in Ru/CoxP@NC is positively shifted comparable with that of metallic Co (778.2 eV), whereas the binding energy (129.4 eV) of P is negatively shifted relative to that of element P (130.2 eV). This undoubtedly proves that a transfer of electron density could occur from Co to P, which is favorable for the HER.[28, 31, 55] In control experiment, the CoxP@NC hybrid was also synthesized under the same condition, but using Co3[Co(CN)6]2 as precursor. The detailed structural characterizations of the obtained samples were analyzed by SEM, TEM, PXRD, and XPS, respectively, as shown in Figures S6-8.


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Figure 4. (a) LSV and (b) Tafel curves of CoxP@NC, Ru/CoxP@NC, and 20% Pt-C. (c) The double-layer capacitance of CoxP@NC and Ru/CoxP@NC electrodes. (d) Current-time chronoamperometric response of Ru/CoxP@NC at 10 mA cm-2. Inset: LSV curves of the Ru/CoxP@NC catalyst before and after 1000 CV cycles. The electrocatalytic activity of Ru/CoxP@NC toward the HER was assessed in N2-saturated 0.5 M H2SO4 solution utilizing a standard three-electrode setup. Firstly, the electrocatalytic HER performance of Ru/CoxP@NC (1.1) and Ru/CoxP@NC (3.3) with different content of Ru (1.1 and 3.3 mL) are also investigated, as demonstrated in Figure S9. The Ru/CoxP@NC shows the best catalytic behavior for the HER. For comparison, CoxP@NC and commercial 20% Pt-C were also studied. As revealed in Figure 4a, the onset overpotential of Ru/CoxP@NC is evaluated to be about 41 mV, slightly higher than that of commercial Pt-C (0 mV). In sharp contrast, the CoxP@NC catalyst shows inferior electrocatalytic ability with relatively larger onset overpotential of 68 mV. In particular, the Ru/CoxP@NC catalyst just needs an overpotential of 165 mV to reach current density of 10 mA cm-2, which is 74 mV lower than that of CoxP@NC (239 mV). Moreover, the Tafel slope of Ru/CoxP@NC is only 54.7 mV dec-1, outperforms that of CoxP@NC (Figure 4b), implying that the HER pathway follows a Volmer-Heyrovsky reaction



mechanism.[25,

31]

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These results are comparable to, even superior to those of some currently

reported electrocatalysts toward HER (Table S1).[24,

28, 33, 56, 57]

The electrochemically active

surface area (ECSA) was assessed according to the double-layer capacitance (Cdl). As can be seen in Figure 4c, the Cdl of Ru/CoxP@NC (1.92 mF cm-2) is 1.58 times higher than that of CoxP@NC (1.21 mF cm-2), which illustrates that the Ru/CoxP@NC catalyst possesses a larger ECSA, contributing to the high-performance HER behavior. The turnover frequency (TOF) value is calculated to be about 0.333 s-1 for the Ru/CoxP@NC at 165 mV. Besides, the electrocatalytic durability of Ru/CoxP@NC was also detected with long-term cycles in 0.5 M H2SO4 solution. Compared to that of commercial Pt-C (Figure S10), 84% of the initial current of Ru/CoxP@NC is maintained after continuous operation of 10 h. Simultaneously, it is clear that the overpotential at 10 mA cm2 is negatively shifted by only 5 mV in comparison with the initial. Especially, the morphology and structural composition of Ru/CoxP@NC could be still remained after the stability measurement (Figure S11). Accordingly, the outstanding electrocatalytic performance and long-term stability make the composite as a promising alternative to Pt-based electrocatalysts toward HER in acid media. Based on the above-mentioned results, the amazing HER catalytic activity of Ru/CoxP@NC could be attributable to the following aspects: (1) the small-sized Ru and CoxP nanoparticles can be regarded as active species for HER.[31, 43, 47] (2) the presence of NC can not only offer large contact area and high conductivity but prevent Ru/CoxP nanoparticles from corroding and oxidizing.[29,

44]

Last but not least, the synergistic effects of Ru/CoxP and NC result in the

enhanced catalytic performance and better durability toward the HER. CONCLUSIONS


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In summary, we have demonstrated a simple synthetic route to explore Ru/CoxP@NC nanocages using Ru-Co3[Co(CN)6]2 as precursor. Thanks to the special structure and composition advantages, the resultant hybrid shows remarkable electrocatalytic properties and stability for the HER, which is compared with some outstanding catalysts reported in acid media. Therefore, these findings open an avenue for the development of MOFs-based high-efficiency and robust electrocatalysts toward HER. ASSOCIATED CONTENT Supporting Information. This material is available free of charge via the Internet at http://pubs.acs.org. Structure and morphology characterizations including SEM, TEM, PXRD, EDX, N2 sorption isotherms and XPS for Co3[Co(CN)6]2 and other control samples in Figures S1-S11. Literature comparison in Table S1.

AUTHOR INFORMATION Corresponding Author E-mail: [email protected] ORCID Ji-Sen Li: 0000-0003-2578-422X Notes The authors declare no competing financial interest. ACKNOWLEDGMENT This work was supported by the Project of Shandong Province Higher Educational Science and Technology Program (No. J16LC02), the Natural Science Foundation of Shandong Province (No.



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Scheme-1 85x93mm (300 x 300 DPI)

ACS Paragon Plus Environment

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Figure-1 85x83mm (300 x 300 DPI)





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Figure-3 85x104mm (300 x 300 DPI)





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Synopsis: A MOFs-derived Ru/CoxP@NC hybrid exhibits efficient electrocatalytic activity and long-term stability toward the HER. 85x78mm (300 x 300 DPI)


Enhanced the Hydrogen Evolution Performance by Ruthenium

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