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Article

Ferrocene Formic Acid Surface Modified Ni(OH)2 for Highly Efficient Alkaline Oxygen Evolution

by
Guo-Ping Shen
1,
Ruo-Yao Fan
1,
Bin Dong
1,* and
Bo Chen
2,*
1
State Key Laboratory of Heavy Oil Processing, College of Chemistry and Chemical Engineering, University of Petroleum (East China), Qingdao 266580, China
2
Department of Chemistry, City University of Hong Kong, Kowloon, Hong Kong, China
*
Authors to whom correspondence should be addressed.
Crystals 2022, 12(10), 1404; https://doi.org/10.3390/cryst12101404
Submission received: 29 August 2022 / Revised: 28 September 2022 / Accepted: 30 September 2022 / Published: 4 October 2022
(This article belongs to the Special Issue Emerging Low-Dimensional Materials)
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Abstract

:
FeNi-based hybrid materials are among the most representative catalysts for alkaline oxygen evolution reaction (OER), but the modulation of their surface atoms to achieve the optimal catalytic properties is still a big challenge. Here, we report the surface modification of Ni(OH)2/nickel foam (NF)-based electrocatalyst with a trace amount of ferrocene formic acid (FFA) (FFA-Ni(OH)2/NF) for highly efficient OER. Owing to the strong electron interaction and synergistic effects of Fe-Ni heteroatoms, FFA-Ni(OH)2/NF exhibits an overpotential of 311 mV at a current density of 100 mA cm−2. Impressively, the overpotential of FFA-Ni(OH)2/NF at 100 mA cm−2 is 108 mV less than that of bulk phase doped Ni/FFA(OH)2/NF, demonstrating the surprising effect of heteroatomic surface modification. In addition, by introducing a small amount of surface modifier into the electrolyte, the weak surface reconstruction process in the electrochemical process can be fully utilized to achieve obvious modification effects. Therefore, this work fully proves the feasibility of improving catalytic activities of FeNi-based catalysts by modifying surface heterogeneous atom pairs.

1. Introduction

Developing sustainable green energy is a key way to realize a low-carbon transition [1,2]. At present, the development of main renewable green energy sources, including solar energy, tidal energy, wind energy, and geothermal energy, are severely limited by their intermittency, instability, and regionalism [3,4,5]. Hydrogen, by contrast, has a high energy density and good sustainability and is emerging as the latest star in the third energy revolution of the world [6,7,8,9].
Compared with traditional industrial hydrogen production, water electrolysis is a more ideal way for hydrogen production because of its advantages, such as being sustainable and pollution-free [10,11,12]. However, the efficiency of hydrogen production from water electrolysis is severely limited by the oxygen evolution reaction (OER) of four-electron transfer that occurs slowly at the anode [13,14,15,16]. At present, the most widely-used catalysts for OER are precious metals and their derivatives such as RuO2 and IrO2, which suffer from their high price and rare reserves [17,18,19,20,21]. It is reported that the well-designed FeNi-based hybrid catalytic materials in an alkaline environment have superior OER performance comparable to that of precious metals [22,23,24,25,26]. However, the key problem limiting the development of FeNi-based hybrid catalysts, especially FeNiOxHy, is that under the action of oxidation current, the strong oxidation and reconstruction of the surface of catalysts, lead to the loss of active sites and stability attenuation [27,28]. Therefore, the design and synthesis of FeNi-based catalytic materials with heterogeneous catalytic surfaces for the long-term OER is still a research hotspot.
Through accidental or intentional Fe doping or incorporation, the OER activity of nickel/cobalt-based electrocatalysts can be greatly increased, which is called the “Fe effect” [29,30,31]. Many researchers have discovered this phenomenon, but few have applied it to the synthesis and development of Fe-Ni and Fe-Co-based bimetallic composites. Furthermore, our previous work has shown that catalytic surfaces rich in nickel and low in iron are more conducive to the bonding of heterogeneous atoms to maintain the long-term stability of FeNi-based hybrid materials [32].
Herein, we synthesized trace ferrocene formic acid (FFA) modified Ni(OH)2 hybrid catalyst by a simple electrochemical activation method to provide excellent OER performance in an alkaline solution. Due to the unique heteroatomic bond cooperation assisted by electrochemistry, the introduction of a small amount of ferrocene formic acid in the electrolyte can significantly improve the reaction current and oxygen evolution efficiency, indicating that it has a good modification effect on Ni(OH)2 catalytic surface. Meanwhile, after ferrocene formic acid was introduced, the solid electronic interactions between Ni and Fe might change the electronic structure of Ni(OH)2 to provide suitable intermediate adsorption energy. Impressively, the OER activity of Ni/FFA(OH)2/NF is far inferior to that of FFA-Ni(OH)2/NF.

2. Experimental Section

2.1. Chemicals

Ni(NO3)2·6H2O (AR), C11H10FeO2 (AR), and C3H7NO (DMF) (AR) were purchased from Macklin (Shanghai, China). We used standard analytical pure KOH (purchased from Sinopharm Chemical Reagent Co., Ltd., Shanghai, China) to prepare the electrolyte. The content of Fe in this KOH is less than 0.001%. Nickel foams (NFs) were ultrasonically cleaned in acetone, hydrochloric acid (1 mol L−1), and ethanol for 30 min. In this experiment, all electrolytes are prepared with specially purified ultrapure water to avoid any impurities. The models of electric heating constant temperature blast drying oven, muffle furnace, and tube furnace are DGG-90030G, KSL-1200X, and ZL-2011-2-0389859.8, respectively.

2.2. Synthesis of the Ni(OH)2/NF

The growth solution contains ammonium fluoride (3 mmol), nickel nitrate (3 mmol), urea (10 mmol), and deionized water (40 mL) [33,34]. The prepared solution was then added to the reactor including a piece of NF (2 cm × 2 cm), and then heated at 100 °C for 12 h. Finally, a color transition of NF from silver-gray to light green can be observed.

2.3. Synthesis of the FFA-Ni(OH)2/NF

FFA-Ni(OH)2 was obtained by rapid electrochemical activation. First, Ni(OH)2/NF was activated to a stable state by linear sweep voltammetry (LSV) (5 mV s−1, 0–0.7 V vs. SCE, 5 cycles). Then, ferrocene formic acid solution (0.05 mol L−1) was added to the electrolyte drop by drop and stirred evenly. At the same time, LSV scanning was continued until stable. Finally, about 40 uL ferrocene formic acid solution was added until achieving the optimum activity. Finally, the obtained FFA-Ni(OH)2/NF catalyst was washed with deionized water.

2.4. Synthesis of the Ni/FFA(OH)2/NF

The synthetic method of Ni/FFA(OH)2/NF is almost the same as that of Ni(OH)2/NF, except that the growth solution is replaced with 10 mL 0.05 mol L−1 ferrocene formic acid solution, nickel nitrate (3 mmol), urea (10 mmol) and deionized water (40 mL).

2.5. Characterization

X-ray diffraction (XRD, Rigaku D/MAX-2500PC) with Cu Kα, λ = 1.54 Å was used to investigate the crystal phase-related information of the obtained catalysts. The instrument models of scanning electron microscopy (SEM) and transmission electron microscopy (TEM) are Hitachi S-4800 and FEI Tecni G20, respectively. The SEM-energy dispersive spectrometer (EDS) was used to analyze the detailed elemental composition of the catalyst. X-ray photoelectron spectroscopy (XPS) was tested on a Thermo Fisher Scientific II spectrometer using an Al Kα source.

2.6. Electrochemical Measurements

The electrochemical activities of catalysts were tested with a Gamry Reference 600 workstation in 1 M KOH electrolyte. In a typical three-electrode system, the working, counter, and reference electrodes are catalysts on NF, platinum sheet, and calomel electrode, respectively. Specifically, the LSV sweep is set at 5 mV s−1; the test voltage and frequency ranges of electrochemical impedance spectroscopy (EIS) are 0.45 V vs. SCE and 105−0.1 Hz; the current density for the chronopotentiometry method is 200 mA cm−2. The electrochemical active surface areas (ECSAs) of electrocatalysts were measured by cyclic voltammetry (CV). Test voltage range was set as 1.35–1.45 V vs. RHE and sweep speeds were set as 20, 40, 60, 80, and 100 mV s−1. Their electrochemical double-layer capacitances (Cdl) were obtained from the change rate of voltage with sweep speed. According to the formula ESCA = Cdl/Cs (Cs = 0.04 mF), the corresponding ECSA of each sample can be obtained.

3. Results and Discussion

Figure 1 shows the detailed synthesis pathway of trace ferrocene formic acid (FFA)-modified Ni(OH)2 electrocatalyst (named FFA-Ni(OH)2/NF), including a one-step hydrothermal reaction and simple electrochemical activation process. It has been reported that Ni(OH)2 has a special bonding effect for Fe ions, and the electrochemical reconstruction process of OER can promote the interaction of Fe-Ni heteroatomic pairs [24,25]. The XRD peaks of pure Ni foam are consistent with the characteristic peaks of standard Ni (00-003-1051) (Figure S1, see Supplementary Materials). Ni(OH)2 synthesized by hydrothermal reaction has a mixed crystal phase structure. As shown in Figure 2a, XRD peaks of Ni(OH)2/NF correspond to the standard peaks of α-Ni(OH)2 (00-038-0715) and β-Ni(OH)2 (01-074-2075). After the surface treatment with ferrocene formic acid, the original crystal structure of Ni(OH)2 was basically retained, and the characteristic peaks of Fe(OH)3 were also detected. This indicates that a tiny proportion of ferrocene is electro-activated to form Fe(OH)3 after electrochemical action due to the particular interaction of Fe-Ni heteroatoms. In alkaline environments, OH intermediates can be adsorbed to Ni-Fe sites by terminal bonding or bridging to form heteroatomic bonds—Fe-O-Ni, which can be pivotal catalytic sites with high OER activity [35,36].
In addition, the near-surface species composition and elemental valence states of all electrocatalysts were characterized by XPS. Characteristic peaks of Ni, O, and Fe appear in the full-range spectral data of FFA-Ni(OH)2/NF (Figure 2b), which is consistent with the XRD data mentioned above. In detail, the Ni 2p peaks of FFA-Ni(OH)2/NF could be divided into four peaks: Ni 2p3/2 (854.83 eV), Ni 2p1/2 (877.42 eV), Sat1 (860.51 eV) and Sat2 (878.40 eV) (Figure 2c). For the Ni 2p spectrum of Ni(OH)2/NF, four similar peaks are located at 855.23, 861.03, 873.03, and 878.94 eV, respectively. A detailed comparison shows that the peak of Ni 2p3/2 of FFA-Ni(OH)2/NF is offset by 0.4 eV relative to Ni(OH)2/NF, indicating an intense electron interaction between the introduced Fe and Ni.
In addition, the O 1s of FFA-Ni(OH)2/NF and Ni(OH)2/NF can be divided into three peaks corresponding to O-M (520 eV), O-H (531 eV), and adsorbed oxygen (532 eV) (Figure 2d). Compared with Ni(OH)2/NF, the M-O peak of FFA-Ni(OH)2/NF also exhibits a 0.3 eV shift, which is also due to the electron interaction of Fe-Ni heteroatom pairs. The 2p profile of Fe is shown in Figure S2. The peak of Fe is puzzling due to the interference of the strong Auger peak of Ni. This may also be caused by too little Fe content on the surface of FFA-Ni(OH)2/NF.
The surface morphology information of electrocatalysts can be obtained from SEM. The surface of the pure NF is smooth, which is not conducive to the exposure of the catalytic active site and the direct application of the catalytic process (Figure S3). However, NF is more suitable for dispersion substrate because of its complex pore structure. In Figure 3a, the Ni(OH)2/NF prepared by the hydrothermal method presents a flower-like three-dimensional structure with the aggregation of ultra-thin nanosheets. Polygonal ultra-thin nanosheets are more conducive to providing a large specific surface area and rich active sites (Figure 3d). Moreover, the interspaces formed by the cross-linking of nanosheets can provide a large number of gas transport channels to promote oxygen desorption. The surface elemental distribution of Ni(OH)2/NF is demonstrated in Figure S4, and it can be found that Ni and O are distributed uniformly on the surface of the nanosheet. As we can see in Figure 3b, after ferrocene formic acid surface modification and electrochemical activation, FFA-Ni(OH)2/NF can still maintain the morphology of flower-like nanosheet clusters, indicating that the main structure of the original precursor will not be damaged by FFA modification. More notably, compared with Ni(OH)2/NF, FFA-Ni(OH)2/NF has a thinner and more uniform nanosheet-like structure (Figure 3e), which may be more conducive to the exposure of active catalytic sites and transport of gas. In addition, FFA was added to the growth solution to prepare bulk phase doped Ni/FFA(OH)2/NF, as shown in Figure 3c. It is not difficult to find that Ni/FFA(OH)2/NF does not possess the flower-like morphology of nanosheet aggregation, which may be because the addition of FFA hinders the crystal growth of Ni(OH)2. In Figure 3f, Ni/FFA(OH)2/NF has a spongy porous structure, which is harmful to providing a large specific surface area and abundant active sites. To better reveal the influence of the morphology of electrocatalysts on the ECSA, we carried out CV tests on all samples (Figure S5). The results show that FFA-Ni(OH)2/NF (37.18 mF cm−2) has the largest Cdl compared with Ni(OH)2/NF (23.36 mF cm−2), Ni/FFA(OH)2/NF (30.55 mF cm−2). The ECSAs of FFA-Ni(OH)2/NF, Ni/FFA(OH)2/NF, and Ni(OH)2/NF are 929.50, 763.75, and 584.00 cm−2, respectively (according to the formula: ESCA = Cdl/Cs). The results of the electrochemical test are consistent with SEM characterizations. SEM-Mapping results further showed that Fe, Ni, and O contained in FFA-Ni(OH)2/NF were uniformly distributed, indicating that the electrochemical activation process could achieve uniform Fe dispersion. The content of the Fe element is really low (atomic content as low as 0.22%, Figure S6), indicating that a small amount of FFA can provide a significant modification effect.
To further highlight the enhanced catalytic effect of surface modification, detailed electrochemical characterizations were carried out for all electrocatalysts in 1 M KOH. In Figure 4a, compared with pure Ni(OH)2/NF, the alkaline OER activity of Ni(OH)2 modified by FFA was significantly improved. This may be due to the strong electron interaction and synergistic catalytic effects of Fe-Ni heteroatoms on the catalytic surface. Meanwhile, a small amount of ferrocene formic acid solution was added to the growth solution to synthesize bulk doped Ni(OH)2 (Ni/FFA(OH)2/NF) as the contrast sample.
As expected, the OER properties of Ni/FFA(OH)2/NF are not ideal. Compared with Ni(OH)2/NF, its overpotential reduces by only 30 mV, while FFA-Ni(OH)2/NF reduces by 138 mV at 100 mA cm−2 (Figure 4b). The excellent modification effect of ferrocene formic acid surface modification can be well proved. In Figure 4g, the electrocatalysts in this work have better performances over several previously reported Fe-Ni-based OER catalysts (Table S1). More importantly, FFA-Ni(OH)2/NF exhibits an overpotential of 350 mV at a current density of 300 mA cm−2, which is 240 mV less than Ni(OH)2/NF. OER reaction kinetics of electrocatalysts can be reflected by the Tafel slope. As we can see in Figure 4c, FFA-Ni(OH)2/NF has the smallest Tafel slope (77.68 mV dec−1), indicating that it has improved OER reaction kinetics. In addition, the system resistance (Rs) and charge transfer resistance (Rct) of the catalytic system were studied by electrochemical impedance spectroscopy (EIS). Our results show that the system resistances of NF, Ni(OH)2/NF, Ni/FFA(OH)2/NF, and FFA-Ni(OH)2/NF are similar, but the Rct of FFA-Ni(OH)2/NF decreases nearly 100 times, which indicates that the electron transfer rate of the catalytic surface is obviously accelerated after surface modification with FFA (Figure 4d). This is probably because of the presence of conjugated electrons in the organic match, which makes the conductivity of the material significantly improved. In conclusion, FFA-Ni(OH)2/NF exhibits surprising OER performances thanks to the electron interaction of Fe-Ni heteroatomic pairs, the surface modification effect of FFA, and the stereoscopic flower structure.
In addition, the stability test of FFA-Ni(OH)2/NF was explored in detail. As exhibited in Figure 4e, after 10,000 cycles of CV, the LSV profiles of FFA-Ni(OH)2/NF basically coincide, indicating that it has excellent cycling stability. More importantly, after 50 h of stability testing, the reaction current of FFA-Ni(OH)2/NF did not decay significantly, proving that it also had preeminent long-term stability (Figure 4f). Due to the interaction of abundant conjugated electron pairs, organic iron may be more conducive to Fe site stabilization than inorganic Fe salt. Importantly, the overpotential of the catalyst in this work is comparable to those of previously reported Fe-Ni-based OER catalysts (Figure 4g and Table S1) [37,38,39,40,41,42,43,44,45,46,47]. Therefore, the performance and stability of FFA-Ni(OH)2/NF will meet the requirements of OER catalysts for future industrial applications.

4. Conclusions

In summary, FFA-Ni(OH)2/NF synthesized by electrochemical activation and surface modification of FFA exhibited excellent OER performances in alkaline solution. Electrochemical tests revealed that FFA-Ni(OH)2/NF only required an overpotential of 311 mV at 100 mA cm−2, which was 138 mV less than that of Ni(OH)2/NF. Moreover, the electrocatalytic activities of Ni(OH)2/NF are stable after 10,000 cycles and up to 50 h of durability test. The excellent and comprehensive properties of FFA-Ni(OH)2/NF may come from the following two aspects: (1) the strong electronic interaction of Fe-Ni heteroatom pairs positively regulates the binding energy of oxygen-containing intermediates. (2) the flower-like structure of Ni(OH)2/NF composed of ultrathin nanosheets is well-maintained after micro FFA surface modification. Our research proves that surface modification is an effective way to achieve the performance enhancement of FeNi-based electrocatalysts.

Supplementary Materials

The following supporting information can be downloaded at: www.mdpi.com/article/10.3390/cryst12101404/s1, Figure S1: XRD of Ni foam; Figure S2: Fe 2p of FFA-Ni(OH)2/NF; Figure S3: SEM images of NF; Figure S4: SEM-Mappings of Ni(OH)2/NF; Figure S5: CVs of (a) FFA-Ni(OH)2/NF, (b) Ni/FFA(OH)2/NF, and (c) Ni(OH)2/NF (at 1.35–1.45 V vs. RHE). (d) Cdl of FFA-Ni(OH)2/NF, Ni/FFA(OH)2/NF and Ni(OH)2/NF; Figure S6: The surface element content statistics of FFA-Ni(OH)2/NF; Table S1: Comparison of the overpotential between the catalyst in this work and the previously reported Fe-Ni based OER electrocatalysts [37,38,39,40,41,42,43,44,45,46,47].

Author Contributions

Methodology, G.-P.S.; data curation, G.-P.S. and R.-Y.F.; formal analysis, G.-P.S. and R.-Y.F.; investigation, B.D.; resources, G.-P.S.; writing—original draft preparation, G.-P.S., R.-Y.F., B.D. and B.C.; writing—review and editing, G.-P.S., R.-Y.F., B.D. and B.C.; supervision, B.D. and B.C.; funding acquisition, B.D. All authors have read and agreed to the published version of the manuscript.

Funding

This work is financially supported by the National Natural Science Foundation of China (52174283).

Data Availability Statement

The date that support the findings of this study are available from the corresponding author upon reasonable request.

Conflicts of Interest

The authors declare no conflict of interest.

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Figure 1. Schematic diagram of the preparation of FFA-Ni(OH)2/NF.
Figure 1. Schematic diagram of the preparation of FFA-Ni(OH)2/NF.
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Figure 2. (a) Typical XRD patterns of Ni(OH)2/NF and FFA-Ni(OH)2/NF. (b) XPS spectra of FFA-Ni(OH)2/NF (red) and Ni(OH)2/NF (blue). (c) Ni 2p and (d) O 1s spectra of FFA-Ni(OH)2/NF and Ni(OH)2/NF.
Figure 2. (a) Typical XRD patterns of Ni(OH)2/NF and FFA-Ni(OH)2/NF. (b) XPS spectra of FFA-Ni(OH)2/NF (red) and Ni(OH)2/NF (blue). (c) Ni 2p and (d) O 1s spectra of FFA-Ni(OH)2/NF and Ni(OH)2/NF.
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Figure 3. SEM images of Ni(OH)2/NF (a,d), FFA-Ni(OH)2/NF (b,e), and Ni/FFA(OH)2/NF (c,f). (g) SEM image and EDX elemental mappings of FFA-Ni(OH)2/NF.
Figure 3. SEM images of Ni(OH)2/NF (a,d), FFA-Ni(OH)2/NF (b,e), and Ni/FFA(OH)2/NF (c,f). (g) SEM image and EDX elemental mappings of FFA-Ni(OH)2/NF.
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Figure 4. (a) LSV, (b) overpotential, (c) Tafel, and (d) EIS of FFA-Ni(OH)2/NF, Ni(OH)2/NF, Ni/FFA(OH)2/NF, and NF. (e) LSV of FFA−Ni(OH)2/NF before and after 10,000 CV cycles. (f) The chronopotentiometry (CP) test at 200 mA cm−2 of FFA-Ni(OH)2/NF in 1 M KOH solution. (g) Comparison of the overpotentials of the catalyst in this work and the previously reported Fe-Ni-based OER catalysts.
Figure 4. (a) LSV, (b) overpotential, (c) Tafel, and (d) EIS of FFA-Ni(OH)2/NF, Ni(OH)2/NF, Ni/FFA(OH)2/NF, and NF. (e) LSV of FFA−Ni(OH)2/NF before and after 10,000 CV cycles. (f) The chronopotentiometry (CP) test at 200 mA cm−2 of FFA-Ni(OH)2/NF in 1 M KOH solution. (g) Comparison of the overpotentials of the catalyst in this work and the previously reported Fe-Ni-based OER catalysts.
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Shen, G.-P.; Fan, R.-Y.; Dong, B.; Chen, B. Ferrocene Formic Acid Surface Modified Ni(OH)2 for Highly Efficient Alkaline Oxygen Evolution. Crystals 2022, 12, 1404. https://doi.org/10.3390/cryst12101404

AMA Style

Shen G-P, Fan R-Y, Dong B, Chen B. Ferrocene Formic Acid Surface Modified Ni(OH)2 for Highly Efficient Alkaline Oxygen Evolution. Crystals. 2022; 12(10):1404. https://doi.org/10.3390/cryst12101404

Chicago/Turabian Style

Shen, Guo-Ping, Ruo-Yao Fan, Bin Dong, and Bo Chen. 2022. "Ferrocene Formic Acid Surface Modified Ni(OH)2 for Highly Efficient Alkaline Oxygen Evolution" Crystals 12, no. 10: 1404. https://doi.org/10.3390/cryst12101404

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