Metal Organic Framework Derived Fe-doped CoSe2 Incorporated in

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Metal Organic Framework Derived Fe-doped CoSe2 Incorporated in Nitrogen-doped Carbon Hybrid for Efficient Hydrogen Evolution Xiaolin Wu, Song Han, Denghong He, Chunlin Yu, Chaojun Lei, Wei Liu, Guokui Zheng, Xingwang Zhang, and Lecheng Lei ACS Sustainable Chem. Eng., Just Accepted Manuscript • DOI: 10.1021/ acssuschemeng.8b00968 • Publication Date (Web): 08 Jun 2018 Downloaded from http://pubs.acs.org on June 8, 2018

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ACS Sustainable Chemistry & Engineering

Metal Organic Framework Derived Fe-doped CoSe2 Incorporated in Nitrogen-doped Carbon Hybrid for Efficient Hydrogen Evolution Xiaolin Wu†, Song Han‡, Denghong He†, Chunlin Yu†, Chaojun Lei†, Wei Liu†, Guokui Zheng†, Xingwang Zhang*, †, Lecheng Lei† †

Key Laboratory of Biomass Chemical Engineering of Ministry of Education, College of

Chemical and Biological Engineering, Zhejiang University, Hangzhou 310027, PR China ‡

School of Environment and Safety Engineering, Jiangsu University, Zhenjiang 212013, PR

China * E-mail: [email protected]

ABSTRACT:

Developing cost-efficient hydrogen evolution reaction (HER) electrocatalysts for water splitting has long been a big challenge. Here, a hybrid of Fe doped CoSe2 incorporated in nitrogen doped carbon (Fe-CoSe2@NC) was synthesized by selenization of Fe3+-etched metal organic frameworks (ZIF-67). As a result of the electronic structure engineering and morphology designing, the Fe-CoSe2@NC hybrid showed an enhanced HER performance with a low overpotential of -143 mV for 10 mA cm-2and a small Tafel slope of ~40 mV dec-1. It also exhibited good stability and a high Faradiac efficiency. The enhanced HER activity might be

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owing to the increased active surface area due to Fe3+ ions etching. Moreover, the density functional theory (DFT) calculations indicate that the improved HER activity of Fe-CoSe2 could be attributed to the favorable adsorption–desorption behavior and accelerated HER kinetics, which was induced by the doping of iron atoms into CoSe2. This work comes up with a valuable strategy in designing and improving advanced electrocatalysts.

KEYWORDS: MOFs derived, hydrogen evolution, Fe-doped CoSe2, DFT calculation

INTRODUCTION

The excessive use of traditional fossil fuels has resulted in a series of environmental issues, and hydrogen has been perceived as an ideal alternative to solve these problems because it’s totally clean and renewable.1-3 Among various approaches to generate hydrogen, electrolysis of water is the most attractive one due to the economical and environmental benefits. Even though platinum is acknowledged as the most active electrocatalyst for HER, its high price largely limits its applications in the industry.4 Thus, the exploration of HER electrocatalysts with high efficiency and cost-effective elements have attracted extensive concerns.5 In the past few years, various electrocatalysts including carbon-based catalysts,6-8 metal alloys,9-10 metal carbides,11-12 metal nitrides,13 metal dichalcogenides,14-19 metal phosphides,20-22 etc. have emerged. Among these earth-abundant materials, the pyrite-type transition metal dichalcogenides (TMDs), which were inspired by the mechanism and special structure of hydrogenase, have been identified as a class of promising HER electrocatalysts due to its diverse electronic structures and chemical composition tunability.23-25 In order to fully utilize the electrocatalytic properties of pyrite-type material, various routes have been developed, such as fabricating nanocomposites with large active surface areas,26-28 homogeneously dispersing catalysts on conductive supports,29 2 Environment ACS Paragon Plus

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increasing the exposed active edge sites,30 tuning the electronic structure on the molecular scale,31-33 etc. Chemical doping is an important strategy in electronic structure engineering, which can largely increase the conductivity and the number of active sites.24, 34 Xie et al. found that the introduction of nitrogen atoms in the CoS2 system optimized the Gibbs free energy for active sites, thus facilitating the HER kinetics.35 Xia et al. found that transition-metal doping is an effective method to optimize the energy level of electrocatalyst and improve the HER catalytic activity.36 Metal-organic frameworks (MOFs) are constructed by strong chemical bonds between organic ligands and metal ions or clusters,37-39 which are ideal precursors or platforms for the preparation of diverse functional materials with designable structures and compositions. The delicate MOFs have many advantages including integrated network of carbon matrix, various heteroatoms providing more active sites, homogeneously distributed metal atoms and welldefined morphology.40-41 These features make them widely used in the synthesis of metal/carbon-based catalysts, such as the graphene-tube–rich N-Fe-MOF catalysts,42 hybrid Co3O4@C-MWCNT,43 ZnO quantum dots coated with porous carbon,44 Fe-Co alloys encapsulated

in

N-graphene

layers,45

onion-like

graphene

layers

encapsulating

Ni

nanoparticles,46 etc. Among various MOFs, zeolitic imidazolate frameworks (ZIFs) have emerged as one of the most popular class for electrocatalysts precursor, because they have tunable structures and versatile functionalities, and are abundant with nitrogen, carbon and transition metal elements.47-48 Moreover, during the conversion process to MOF derivatives, ZIFs can serve as a nitrogen-doped source as well as non-noble metal catalyst precursor, resulting in a favorable N-doped carbon matrix supporting metal catalysts with excellent electrical properties and abundant active sites,49-50 thereby enhancing electrocatalytic activity.51



In this work, we designed a novel hybrid of Fe-doped CoSe2 incorporated in nitrogen-doped carbon by the facile two-step method. The ZIF-67 was etched by Fe3+ ions, then followed by a thermal selenization process, after which Fe atoms were successfully doped into CoSe2 and incorporated in N-doped carbon (NC) matrix as well. The distinct ZIF-67 precursor contributes to the conversion of nitrogen rich carbon support with porous structure and large surface area, which would also assist in electrocatalytic activity. The obtained Fe-CoSe2@NC electrocatalyst showed superior HER activity over the pristine CoSe2@NC. The enhanced HER activity of FeCoSe2@NC would be partly attributed to the larger electrochemical active area. Moreover, the density functional theory (DFT) calculations revealed that Fe-doped CoSe2 possessed an advantageous adsorption free energy of hydrogen and longer bond length, facilitating adsorption–desorption process of intermediate adsorbed hydrogen and accelerating H2 generation. The thermal conversion of etched MOFs method can be also applied to other metaldoping systems, we believe that this work could open a door to the design and modification of high performance electrocatalysts based on MOFs.

EXPERIMENTAL SECTION

Synthesis of ZIF-67 The ZIF-67 sample was prepared by a modified traditional coprecipitation method reported elsewhere.52-53 Typically, 2 mmol Co(NO3)2·6H2O and 8 mmol 2-methylimidazole were dissolved in 50 ml absolute methanol to form transparent solution, respectively. Then, the 2methylimidazole solution was poured into the Co(NO3)2 solution under stirring. After 24 h stirring of the mixed solution at normal temperature, the purple precipitate of ZIF-67 was washed with absolute ethanol and separated by centrifugation for 3 times, then dried at 60 oC in the oven


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for 12 h. Synthesis of Fe-ZIF-67 Disperse ZIF-67 (40 mg) in absolute ethanol (20 ml) to from a homogeneous purple dispersion, then add 5-20 mg Fe(NO3)3·9H2O solution (dissolved in 5 ml absolute ethanol) into the former dispersion slowly. After stirring for 1h under room temperature, the product of FeZIF-67 was also washed, filtrated and dried as ZIF-67. Synthesis of Fe-CoSe2@NC The obtained Fe-ZIF-67 was carbonized and selenized by annealing with Se vapor at different temperatures in a home-made tube reactor using Ar (100 sccm) as carrier gas. With the effect of high temperature and the Se vapor, the organic frameworks turned into nitrogen doped carbon matrix, and the metal atoms converted into Fe-doped CoSe2. The new composite was defined as Fe-CoSe2@NC. CoSe2@NC sample was derived from pure ZIF-67 with the same process. Fabrication of electrodes Firstly, disperse 50 wt.% Fe-CoSe2@NC powder, 40 wt.% conductive carbon black and 10 wt.% polyvinylidene fluoride (PVDF) binder in isopropanol to form a homogeneous slurry. Then, spread the slurry on CFP substrates with a geometric area of 0.4 cm2 and dried at 50 oC overnight. The net weight of Fe-CoSe2@N-C powder loaded on CFP was ~0.5 mg/cm2. The fabricated CFP electrodes were directly used as cathodes for all electrochemical characterizations.

RESULTS AND DISCUSSION

The schematic depicting the preparation of Fe-CoSe2@NC is shown in Figure 1d, along



with the scanning electron microscopy (SEM) images (Figures 1a-c) of different products at each step. ZIF-67 was prepared via a co-precipitation method under room temperature, and it exhibited distinct topological features with rhombic dodecahedron structure (Figure 1a). ZIF-67 was then treated with different amounts of iron nitrate under fierce stirring to obtain Fe3+-etched ZIF-67 (Fe-ZIF-67, Figure 1b). When the iron nitrate was added into the ZIF-67 dispersion solution, protons generated from the hydrolysis of Fe3+ ions will slowly etch ZIF-67, leading to the releasing of Co2+, meanwhile, with the consumption of protons, the amount of hydroxy ions increased, Co2+ ions and Fe3+ ions co-precipitate in ZIF-67 to form Fe-ZIF-67.54-55 The atomic ratio of Fe/Co in Fe-ZIF-67 is ~3.2 % (analyzed by energy dispersive spectroscopy in Figure S1, see SEM images of Fe-ZIF-67 with different Fe/Co ratios in Figure S2). The inductively coupled plasma optical emission spectrometry (ICP-OES) analysis was also adopted to gain accurate content of Co and Fe, the calculated Fe/Co atomic ratio was 2.96 %, quite close to result of EDS. The surface of the polyhedron turned tough after Fe3+ ions etching, which might introduce more pores to the polyhedron. Afterwards, the Fe-ZIF-67 was selenized with Se vapor at 400 oC to obtain Fe-CoSe2@NC hybrid dodecahedron (Figure 1c).


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Figure 1. (a)-(c) SEM images of ZIF-67, Fe-ZIF-67 and Fe-CoSe2@NC. (d) Schematic illustration of the synthesis process of Fe-CoSe2@NC, involving Fe3+ etching of ZIF-67 and the following thermal selenization. The structure of sample was also carefully elucidated with transmission electron microscopy (TEM). TEM image in Figure 2a reveals the general hexagon projected shape of the Fe-ZIF-67, corresponding with the SEM images. After thermal selenization at 400 oC, the synthesized Fe-CoSe2@NC shows similar morphology in Figure 2b, the regular hexagon with bold edges clearly reveal the rhombic dodecahedron structure, indicating that the morphology preserved well after the above two steps. The high resolution TEM (HRTEM) investigation of Fe-CoSe2@NC is shown in Figure 2c (inset is the fast Fourier transform pattern), the resolved lattice fringes of (111) plane with a spacing of 2.59 Å demonstrating the orthorhombic structured of pyrite CoSe2 (consistent with that of CoSe2@NC shown in Figure S3). Energy dispersive spectroscopy (EDS) mapping was performed to explore the spatial distribution of different



elements as shown in Figure 2d. It’s obvious that Fe element uniformly distributes in the whole dodecahedron with a relatively low density. The powder X-ray diffraction (XRD) patterns of ZIF-67, Fe-CoSe2@NC are illustrated in Figure 2e for the further investigation of crystal structures (XRD results of Fe-ZIF-67 in Figure S5). The diffraction peaks at 34.5 o, 35.9 o, 47.7 o, 50.2 o, 53.5 o, 56.9 o and 63.3 o can be well indexed to (111), (120), (211), (002), (031), (131) and (122) planes of CoSe2 (JCPDS No. 53-0449),56 respectively, which suggest the formation of orthorhombic structured CoSe2 after selenization process. The valence and chemical composition of Fe-CoSe2@NC were investigated by X-ray photoelectron spectra (XPS) as shown in Figures 2f-h. In Figure 2f, the peaks at 710.4 eV and 723.2 eV could be assigned to Fe 2p3/2 and Fe 2p1/2, accompanying with the satellites at around 715.8 eV and 718.6 eV, together reveal the existence of Fe2+ doping in pyrite-phase and some higher oxidation state of Fe species.57-58 That’s because the obtained carbon matrix was reductive under high temperature in inert atmosphere, thus, the majority of Fe3+ ions were reduced to Fe2+ by carbon and doped in CoSe2 crystal. For Co 2p, the binding energy of Co 2p3/2 at ~778 eV and Co 2p1/2 at ~793 eV correspond to Co2+ cations in CoSe2.59-60 In the region of Se spectrum, the broad peak at ~55 eV belongs to Se 3d5/2 and 3d3/2, indicating the presence of Co-Se bond, which is also consistent with CoSe2, and the peak at ~59 eV is related to the bonding structures of Co 3p and SeO2.61-62 The characteristic peaks of Co 2p and Se 3d spectra are similar with the CoSe2@NC sample (Figure S8). The structure of the hybrid is also revealed by Raman spectra for further investigation (Figure S9), also confirm the structure of orthorhombic CoSe2. All above characterizations clearly indicate the successfully synthesized Fe doped CoSe2 incorporated in the N-doped carbon matrix.


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Figure 2. (a) TEM image of Fe-ZIF-67. (b) TEM image of Fe-CoSe2@NC. (c) HRTEM image of Fe-CoSe2@NC and the corresponding FFT pattern as inset. (d) EDS elemental mapping images of Fe-CoSe2@NC. (e) XRD results of ZIF-67, Fe-CoSe2@NC. XPS spectra of FeCoSe2@NC for (f) Fe 2p, (g) Co 2p and (h) Se 3d. To explore the structure-function relationship of electrocatalysts, the HER activity of optimized Fe-CoSe2@NC sample selenized at 400 oC with Fe/Co atomic ratio of 3.2 % was detailed demonstrated. All catalyst powders were made into slurry and brushed onto the carbon fiber paper to fabricate electrodes for electrochemical measurements in a three-electrode cell



filled with 0.5 M H2SO4 solution. The Fe-CoSe2@NC samples selenized under different temperatures with different doping ratios were also studied for comparison (see Figures S4, S6, S11-12). Polarization curves with iR correction were illustrated in Figure 3a, the Fe-CoSe2@NC electrode exhibits excellent HER activity with low overpotentials of -143 mV and -184 mV to achieve -10 and -100 mA cm−2, respectively, which are considerably lower than the pristine CoSe2@NC electrode (-173 mV and -250 mV, respectively). To gain a direct understanding of the intrinsic HER activities of the electrocatalysts, the Tafel slope, which is calculated from polarization curves, is summarized in Figure 3b. The Tafel slope of Fe-CoSe2@NC is only 40.9 mV dec-1, which is obviously lower than that of CoSe2@NC (69.2 mV dec-1), proving highly competitive performance among these efficient TMDs electrocatalysts (Table S1). Besides, the low Tafel slope indicates that the Volmer reaction of HER is operative with the catalysis of FeCoSe2@NC, and the rate-limiting step would be Heyrovsky or Tafel reaction.63-64 Stability is another crucial evaluation indicator for HER electrocatalysts, therefore, a 48-hour continuous galvanostatic measurement is performed at -10 mA cm-2 in 0.5 M H2SO4 to test the durability of Fe-CoSe2@NC. In Figure 3c, the overpotential maintains at ~-150 mV and no obvious fluctuation occurs during the whole test, demonstrating the excellent stability of Fe-CoSe2@NC towards HER. The electrochemical impedance spectroscopy (EIS) was applied to explore the charge-transfer mechanism of HER on these samples. Figure 3d shows the Nyquist plots of CoSe2@NC and Fe-CoSe2@NC. It is found that the electrode system can be equivalent to a typical simplified Randles Cell model. The Rct values of Fe-CoSe2@NC decreased remarkable after Fe-doping, show the same trend of Tafel slopes, suggesting a smaller charge-transfer resistance and facile kinetics toward hydrogen evolution.65 Furthermore, we employed cyclic voltammetry (CV) to evaluate the electrochemical double-layer capacitance (Cdl) by sweeping at


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non-faradaic potentials. Generally speaking, Cdl is expected to show obvious positive correlation with catalytically effective surface areas in HER, which may greatly influence the catalytic performance. As illustrated in Figure S10. The Cdl of Fe-CoSe2@NC (32.5 mF cm-2) is much higher than the CoSe2@NC (21.6 mF cm-2), implying a larger effective surface area toward HER. Furthermore, we measured the Faradaic efficiency of H2 generated on Fe-CoSe2@NC cathode by collecting the gas products and analysing with gas chromatography. It is interesting seen that the Faradaic efficiency is quite close to 100% (see Figure S14), indicating excellent electrocatalytic activity toward HER and negligible side reactions.

Figure 3. (a) LSV polarization curves and corresponding (b) Tafel plots of Fe-CoSe2@NC and CoSe2@NC. (c) Chronopotentiometric measurement of Fe-CoSe2@NC at -10 mA cm-2. (d)



EIS Nyquist plots of Fe-CoSe2@NC and CoSe2@NC and fitted solid traces; inset: the equivalent circuit. The Fe-doping action not only changes the morphology and the composition, it may also modulate the electronic structure of CoSe2 and affect the reaction thermodynamics of hydrogen evolution.36 To illustrate the fundamental mechanism of the significant improvement of HER activity on Fe-CoSe2@NC, we applied density function theory (DFT) calculations to study the effects of iron incorporation. In Figure 4a, the continuous and large distribution of the density of states (DOS) go across the Fermi level, which suggests the metallic state of Fe-CoSe2 with high electrical conductivity (see DOS of pure CoSe2 in Figure S15). Generally, three states was summarised during the HER process in acid medium: H+ state, the intermediate H* state and the catalyst-1/2 H2 state.66 Gibbs free-energy of the intermediate adsorbed hydrogen (∆GH*) is an important criterion of HER activity for catalysts, and a small ∆GH* close to zero represents the ideal free energy change between intermediate H* state and the final catalyst-1/2 H2 state, suggesting good HER activity.67-68 In Figure 4b, the ∆GH* of pristine CoSe2 was 0.41 eV on Co site, however, after doping with Fe, the ∆GH* dropped to 0.34 eV, indicating that the Co atoms in Fe-CoSe2 were activated by Fe dopants. The bond length H*-Co on Co site of Fe-CoSe2 was 1.50 Å, longer than the 1.485 Å of H*-Co on the Co sites of pure CoSe2, which indicated a relatively weak bonds on the Fe-CoSe2, thus in favour of the formation of H−H by the recombination of

two adjacent H*.69

Therefore, all calculated results indicate that the

meliorative electron structure induced by iron doping possess an enhanced intrinsic HER activity, concurring with our electrochemical experimental observations.


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Figure 4. (a) Projected density of state of Fe-doped CoSe2. (b) Calculated free-energy diagrams of the HER for pristine CoSe2 and Fe-doped CoSe2; inset: molecular structures with H adsorption on Co site of CoSe2 (right) and Fe-CoSe2 (left), the pink, yellow, cyan and red spheres represent Fe, Se, Co and H atoms, respectively. Based on the above analysis of metal ion doping affects, we go a step further on the Nidoping and Mn-doping orthorhombic CoSe2 electrocatalysts, the HER activity could also be enhanced obviously through similar etching-thermal conversion strategy (Figures S7 and S13), which could be a general method to improve HER activity on congeneric electrocatalysts.

CONCLUSIONS

In conclusion, we have reported the Fe-CoSe2@NC hybrid synthesized by the selenization of Fe3+-etched ZIF-67 as a high-performance HER eletrocatalyst. The Fe-CoSe2@NC hybrid exhibits an enhanced HER activity, with a low overpotential and a small Tafel slope. We demonstrate from both experiments and DFT calculations that transition metal atoms doping can be a significant approach to modulate the electronic structure of pyrite-type electrocatalysts, thus improving the electrocatalytic performance. Moreover, MOFs provide ideal platform for the



modification and conversion of electrocatalysts with diverse compositions and structures. This work gives an insight into new strategies for designing and improving HER electrocatalysts based on earth-abundant pyrite-type TMDs.

ASSOCIATED CONTENT

The Supporting Information is available free of charge on the ACS Publications website at DOI: Experimental section, calculation details, extra SEM, TEM pictures, XRD and XPS results, Raman results, CV curves, polarization curves and calculated results. AUTHOR INFORMATION Corresponding Authors * E-mail: [email protected] Notes The authors declare no competing financial interest. ACKNOWLEDGMENT This research was also supported by China Major Science and Technology Program for Water Pollution Control and Treatment (2017ZX07101003), Natural Science Foundation of Zhejiang Province under Grant No. LR17B060003. The financial support was received from the National Natural Science Foundation of China (Project Nos. 21522606, 21676246, 21476201, 21436007, U1462201, and 21776248). REFERENCES


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Abstract Graphic

The novel hybrid of Fe-doped CoSe2 incorporated in nitrogen-doped carbon derived from MOFs showed enhanced hydrogen evolution reaction performance.


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Metal Organic Framework Derived Fe-doped CoSe2 Incorporated in

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