Direct Construction of Mesoporous Metal Sulfides via Reactive Spray

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Direct Construction of Mesoporous Metal Sulfides via Reactive Spray Deposition Technology Yang Wang, Yang Wu, Alireza Shirazi Amin, peter kerns, Jared Fee, Junkai He, Lei Jin, Radenka Maric, and Steven L. Suib ACS Appl. Energy Mater., Just Accepted Manuscript • DOI: 10.1021/acsaem.8b02110 • Publication Date (Web): 17 Jan 2019 Downloaded from http://pubs.acs.org on January 18, 2019

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Direct Construction of Mesoporous Metal Sulfides via Reactive Spray Deposition Technology Yang Wang,‡,3,4 Yang Wu,‡,1 Alireza Shirazi Amin,2 Peter Kerns,2 Jared Fee,2 Junkai He,1 Lei Jin,2 Radenka Maric,*,3,4 and Steven L. Suib*,1,2 1 Institute

of Materials Science, University of Connecticut, 97 North Eagleville Road, Storrs, Connecticut 06269, United States 2 Department of Chemistry, University of Connecticut, 55 North Eagleville Road, Storrs, Connecticut 06269, United States 3 Department of Materials and Engineering, University of Connecticut, 97 North Eagleville Road, Storrs, Connecticut 06269, United States 4 Center

for Clean Energy Engineering, University of Connecticut, 44 Weaver Road Unit 5233, Storrs, Connecticut 06269, United States

ABSTRACT: A rapid one-step flame combustion deposition method was developed to fabricate the mesoporous metal sulfides directly on nickel foam without binder and template. The first-row transition metal sulfides, Co9S8, Ni3S4, NiCo2S4 and FeS, were successfully synthesized with three-dimensional architecture, large specific surface area (around 110 m2 g-1), and interconnected pore networks. The binary meso-NiCo2S4 exhibited a high specific capacitance (1350 F g-1 at 10 A g-1), excellent rate capability and robust cycling stability in both three-electrode half-cells and asymmetric supercapacitor. This study demonstrated a new scalable strategy to obtain mesoporous metal sulfides with high electrochemical performance.

Key words: mesoporous, sulphides, one-step, template-free, binder-free, RSDT. With a rise in burning of fossil fuels, the atmospheric concentrations of greenhouse gases are increasing and adversely affecting the climate. To solve this problem, the development of clean energy is extremely urgent. Over the past few decades, major concerns have been raised over metal oxides for energy conversion, electrocatalysis, photocatalysis and their hybrid applications.1 However, the poor electronic conductivity, chemical and structural instability limit their performance in electrochemistry.2-3 Compared with metal oxides, metal sulfides are more attractive due to their superior electronic conductivities.4-5 Recently, transition metal sulfides have been intensively studied in metal ion batteries,6-7 supercapacitors,4-5, 8 water splitting,9-10 and CO2 reduction.11-12

the transport of guest species through bulk materials and relieve the structure strain during volume expansion caused by redox reaction, respectively.1 Remarkable efforts have been made on the synthesis of mesoporous metal sulfides.13-23 The initial attempts are made through soft templating approaches, sol-gel, and aerogel.13-16, 18-19 Mesostructures are retained after the removal of surfactant templates. However, the obtained mesopores through a soft-template approach are not highly ordered and, without the support of surfactants, the collapse of mesostructure may happen. To obtain highly ordered mesoporous metal sulfides, the most commonly applied synthetic procedure is nanocasting, using mesoporous silica as a hard template.17, 20-23 With the support of thermally stable hard templates, the effective fabrications of high crystalline mesoporous metal sulfides are achieved. Although mesoporous metal sulfides can be synthesized by template-supporting approaches, their industrial scaling-up is limited by complex time-consuming steps and batchprocessing.24 Reactive spray deposition technology (RSDT), a flame combustion synthetic route in the open atmosphere, is a potential alternative to streamline the synthesis of mesoporous metal sulfides. RSDT is capable of synthesizing nanoparticles of carbon or oxides by continuous deposition on the desired substrates.25-26 The in-situ annealing is accomplished by the high combustion heat from the flame and thus eliminates the need for any further heat treatment. However, subject to the high combustion temperature and oxidizing atmosphere, no attempt has been made on the RSDT synthesis of metal sulfides, especially mesoporous metal sulfides.

Among all metal sulfides, one aspect of particular interest is mesoporous metal sulfides. The advantages of mesoporous materials are ultrahigh surface areas, tunable mesopores and large pore volumes, which increase the active surface, enhance

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Figure 1. (a) Schematic illustration of the reactive spray deposition of mesoporous metal sulfides, (b) SEM and TEM images of mesoCo9S8, (c) SEM and TEM images of meso- Ni3S4, and (d) SEM and TEM images of meso-NiCo2S4. To tackle this challenge, we customized components and configurations of RSDT, accommodating the formation of mesoporous metal sulfides in reactive flames. Typically, a homogeneous solution that contains organometallic precursors and highly combustible thiourea-dissolved solvents are fed through an atomization nozzle. The resulting aerosol spray is ignited to generate a jet-diffusion flame (Figure S11). The reactions between thiourea and water in the high temperature environment produce H2S, CO2, and NH3.27-28 The organometallic precursor rapidly decomposes, followed by the phase transition to vapor. The homogeneous reactions between metal ions and H2S to form metal sulfide particles occur within a few milliseconds. To prevent the oxidation of metal species, a quartz shroud with continuously flowing nitrogen shield gas is employed to isolate the flame from the ambient environment. Detailed experimental procedures are described in the Supporting Information. As shown in Fig. 1a, the mechanisms responsible for the formation and growth of sulfide particles during time-of-flight, are nucleation, coagulation, surface growth, cluster formation, coalescence, and agglomeration. The mesopores of metal sulfides are created by the produced gases during the pyrolysis of organic precursors.25-26 Here we demonstrate the first synthesis of mesoporous Ni3S4, Co9S8 and NiCo2S4 through a template-free RSDT route. Preliminary electrochemical studies confirmed the as-prepared mesoporous metal sulfides exhibit high specific capacitance and stable cycling performance. Wide-angle Powder X-ray diffraction (PXRD) was first carried out to investigate crystallinity and phases of the as-

prepared metal sulfides. Unlike the low-crystallinity typically observed in mesoporous metal sulfides made by softtemplating or other template-free methods, the obtained XRD patterns (Figure S1 and S7a) show that the mesoporous metal sulfides prepared by RSDT are highly crystalline. All recorded diffraction peaks are indexed to the cubic phase Co9S8 (JCPDS 86-2273), Ni3S4 (JCPDS 47-1739), NiCo2S4 (JCPDS 20-0782), and FeS (JCPDS 023-1123), respectively. There is no secondary phase present in all three XRD patterns. In addition, the selected area electron diffraction (SAED) patterns (Figure S2) acquired by transmission electron microscopy (TEM) confirm the identification of the metal sulfides from XRD analysis. The well-defined concentric diffraction rings indicate the polycrystalline nature of the as-made mesoporous sulfides. The surface morphologies of the as-synthesized mesoporous metal sulfides directly deposited on nickel foam are examined by scanning electron microscopy (SEM). The representative SEM images (Figure 1b, 1c, 1d and S7b) show that the mesoporous metal sulfides have almost identical coralreef-like features, which can be attributed to the same processing conditions applied during the synthesis by RSDT. The secondary particles composed of nanoparticle building blocks and the network of interconnected pores are uniformly distributed throughout the substrates, forming disordered macropores. TEM images (Figure 1b, 1c, 1d and S7b) reveal the representative microstructure of the mesoporous metal sulfides synthesized by RSDT. Uniform mesopores are formed by the nanoparticle building blocks. The graphical analysis of the TEM images yield the narrow pore-size distributions,

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ACS Applied Energy Materials around 5 nm, within the particles. The mesopores observed within the nanoparticle building blocks and the network of macropores created by the low degree of fractal connectivity between those blocks constitute the hierarchical porous nanostructure of the metal sulfides prepared by RSDT. Nitrogen sorption was assessed to confirm the mesoporosity of as-synthesized metal sulfides. The corresponding IV-type isotherms with H3-type hysteresis loops are shown in Figure S4a and Figure S7c. The cylindrical geometry of the pores is evidenced by the upward hysteresis in the isotherms. The pore-size distributions derived by Barrett−Joyner−Halenda (BJH) method are rather narrow. The average pore diameters are from 4 to 6 nm (Figure S4b and S7c), proving the uniform mesoporous nanostructures of all three metal sulfides. Benefitting from the uniform mesopores, the mesostructured metal sulfides yield high Brunauer−Emmett−Teller (BET) surface areas that range from 100 to 120 m2 g−1, which are similar to all reported metal

This material shows slightly more Co2+ characteristic based on peak splitting and areas of the Co 2p3/2 and Co 2p1/2 peaks indicative of Co2+. Ni 2p high resolution spectra of mesoNiCo2S4 (Figure 2c) display nickel in a mixed oxidation state as well, exhibiting both Ni2+ and Ni3+ characteristics with the first principle Ni 2p3/2 peak at 853.6 eV and the second at 855.6 eV.29 The Ni 2p doublet separations of 17.2 eV and 17.7 eV are indicative of a mixed valence of Ni2+ and Ni3+.5 Based off the peak areas, there is slightly more Ni3+ present than Ni2+. As for meso-Ni3S4, the Ni 2p high resolution spectra exhibit two oxidation states of Ni, Ni2+ with a principle Ni 2p3/2 peak

Figure 3. Electrochemical characterization of meso-Co9S8, Ni3S4 and NiCo2S4 in three-electrode cells. (a) Cyclic voltammograms at a scan rate of 10 mV s-1,(b) Galvanostatic charge-discharge curves at a rate of 10 A g-1, (c) Rate performance (2 to 20 A g-1), and (d) Long-term cycling performance of meso-NiCo2S4 at 10 A g-1.

Figure 2. (a) XPS spectra of Co 2p of meso-Co9S8 and mesoNiCo2S4, (b) XPS spectra of S 2p of meso-Co9S8, meso-Ni3S4 and meso-NiCo2S4, and (c) XPS spectra of Ni 2p of meso-Ni3S4 and meso-NiCo2S4. sulfides with high surface area (Table S1). To understand elemental properties of as-prepared mesoporous metal sulfides, the elemental distributions were performed by Energy-dispersive X-ray spectroscopy (EDS). As shown in Figure S5, the EDS maps indicate the uniform elemental distribution of all three metal sulfides, which agrees with the presented PXRD patterns of unique phases of each metal sulfide. Moreover, to further understand the chemical states of metals in as-prepared mesoporous metal sulfides, Xray photoelectron spectroscopy (XPS) was utilized. As shown in Fig. 2a, for meso-NiCo2S4, the Co 2p high resolution spectra reveals that Co is in a mix of two different oxidation states, Co2+ with a principle Co 2p3/2 peak position of 778.9 eV and Co3+ with a peak position of 779.8 eV. Based off peak area and the finger print of the two satellite peaks, more Co3+ is present than Co2+ in meso-NiCo2S4. For meso-Co9S8, the Co 2p high resolution spectra (Figure 2a) reveal another mixed oxidation state for Co2+ and Co3+ at 778.9 eV and 780.2 eV, respectively.

position of 853.5 eV and Ni3+ with a peak position of 855.7 eV (Figure 2c). The electrochemical performance of as-prepared mesoporous metal sulfides (meso-Co9S8, Ni3S4 and NiCo2S4) in alkaline electrolyte solution (1M KOH) were first investigated in the three-electrode configuration. The resulting cyclic voltammetry (CV) curves show distinct pairs of redox peaks that correspond to the reversible Faradaic redox processes (Figure 3a). The anodic peak shifts to more positive potential when the concentration of Ni species increase, since the oxidation process of Ni2+/Ni3+ redox couple occurs at a higher potential than that of the oxidation process of Co2+/Co3+/Co4+ redox couple. Meanwhile, meso-NiCo2S4 exhibits the highest redox peak intensity among the three samples, which corresponds to its highest electrochemical activity. Chronopotentiometry (CP) at 10 A g-1 confirms that mesoNiCo2S4 has the highest specific capacitance of 1350 F g-1 (Figure 3b). The CP curves appear to be symmetric and iR-drop in the discharge curves is almost negligible, which serve as indications of good electronic conductivity and high coulombic efficiency of the mesoporous metal sulfides.4-5 In addition, the specific capacitance obtained by meso-Ni3S4 and meso-Co9S8 are 1219 and 766 F g-1, respectively (Figure 3b). The binarymetal sulfide clearly demonstrates the superior pseudocapacitive properties in comparison to the mono-metal



sulfides.8, 30 We further investigated the rate capability of mesoporous metal sulfides. The capacitance retention ratio is as high as 81% when the cur-rent density increases from 2 to 20 A g-1 (Figure 3c). We also carried out the charge/discharge cycling of meso-NiCo2S4 and a high capacitance ratio of 83% after 5000 charge/discharge cycles is achieved, demonstrating the comparable electrochemical stability with other reported literature (Figure 3d and Table S2). The practical electrochemical performance of mesoNiCo2S4 was investigated in an asymmetric supercapacitor device as the positive electrode. The activated carbon film electrode prepared by slurry-casting methods was used as the negative electrode. Due to the combined contribution from the pseudocapacitance of the mesoporous metal sulfide electrodes and the double-layer capacitance of the carbon electrodes, CV curves of the two-electrode full-cell show the less-defined redox peaks (Fig. S6a) than a three-electrode half-cell8. In the meantime, no distinct voltage plateau is observed in the charge/discharge curves (Figure S6b). The device demonstrates good rate capability with a specific capacitance of 48 F g-1 at 20 A g-1 (Figure S6c). We also evaluated the longterm cycling performance of the asymmetric supercapacitor, which is crucial to the feasibility of the electrodes in the energy storage applications. At 5 A g-1, this system achieves a high capacitance ratio of 70.3% after 10000 charge/discharge cycles (Figure S6e). The capacitance loss is likely resulting from oxide or hydroxide formation upon repeating reactions in the alkaline electrolyte. A Ragone plot of the supercapacitor device is displayed in Figure S6f. A high energy density of 38 Wh kg−1 is achieved at a high-power density of 720 W kg−1. When the power density increases to 15 kW kg−1, an energy density of 16 Wh kg−1 is still available (Figure S6f). In summary, we have developed a one-step template-free flame synthesis route to successfully synthesize mesoporous Ni3S4, Co9S8, NiCo2S4 and FeS with high crystallinity. The electrodes of meso-NiCo2S4 prepared by directly depositing on nickel foam demonstrate high specific capacitance, good rate capability, and stable cycling performance in supercapacitors. RSDT presents an efficient, economical, and scalable pathway to manufacture mesoporous metal sulfides. This practical method is fundamentally important for the synthesis of mesoporous transition metal dichalcogenides.

ASSOCIATED CONTENT Supporting Information TEM images, gas sorption data, EDS elemental maps and practical electrochemical data, experimental procedures and calculations.

AUTHOR INFORMATION Corresponding Author *Email: [email protected]. *Email: [email protected].

Author Contributions ‡Yang

Wang and Yang Wu contributed equally to this work.

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Notes The authors declare no competing financial interests.

ACKNOWLEDGMENT S.L.S is grateful for the funding from the US Department of Energy, Office of Basic Energy Sciences, Division of Chemical, Biological and Geological Sciences under Grant DE-FG0286ER13622.A000. The SEM/TEM studies were performed using the facilities in the UConn/Thermo Fisher Scientific Center for Advanced Microscopy and Materials Analysis (CAMMA).

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Direct Construction of Mesoporous Metal Sulfides via Reactive Spray

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