FeNiMo trimetallic nanoparticles encapsulated in carbon cages as efficient hydrogen evolution reaction electrocatalysts

Abstract

Hydrogen is one of the most desirable alternatives to fossil fuels due to its renewability and large energy density. The electrocatalytic hydrogen evolution reaction (HER) is drawing more and more attention since it can produce H₂ powered by renewable energy. Therefore, efficient and durable electrocatalysts are an urgent need. On the one hand, the high price and low reserve of noble metals hinder their further applications. On the other hand, various non-noble metal electrocatalysts cannot achieve satisfactory stability and efficiency. Thus, this paper reports a cheap and feasible way to synthesize a carbon cage-encapsulated FeNiMo compound. It exhibits the desired overpotentials of 199 mV at 10 mA cm⁻² in an alkaline solution and 246 mV at 10 mA cm⁻² in an acidic solution. Besides, it exhibits similar current density loss to commercial Pt/C after 10 000 CV cycles, which suggests satisfactory durability.

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1. Introduction

The increasing greenhouse effect has aroused increasing attention towards renewable energy source conversion and storage.¹ Hydrogen is considered as one of the most desirable alternatives to fossil fuels.² The electrocatalytic hydrogen evolution reaction (HER) can produce H₂ powered by renewable energy, including solar or wind energy.^3,4 In order to drive HER with a lower overpotential, efficient and durable electrocatalysts are an urgent need.⁵ Although noble metals such as Pt, Ir and Ru are used as mainstream electrocatalysts, their high cost and low abundance hinder their further applications.⁶ Therefore, the use of low-cost and earth-abundant electrocatalysts to replace noble metal catalysts is necessary.^7–9 Recently, many transition metals and their compounds have been used as non-noble electrocatalysts, including transition metal oxides,¹⁰ sulfides,^11–14 phosphides,^15–20 carbides,²¹ and nitrides.²² Among them, the compounds based on Co, Fe and Ni are most frequently used as electrocatalysts for HER due to their low cost and deficient 3d electron structures.^23–25 However, due to their weak electronic conductivity and stability, the electrocatalysts based on Fe, Ni and Co are still not able to compete with noble-metal-based electrocatalysts.²⁶ Therefore, we aim to solve these issues in two ways. First, we can establish unique carbon nanostructures, such as carbon nanotubes²⁷ and graphene,²⁸ to enhance the conductivity and stability morphologically. Second, we can combine the metals (Mo) on the left half of the transition metals in the periodic table with the metals (Fe and Ni) on the right half of the series with more filled d-bands, which can build well-pronounced synergism in electrocatalysis.²⁹

In this paper, we report a new Fe, Ni and Mo trimetallic compound encapsulated in a carbon cage as an efficient HER electrocatalyst. This material was synthesized by a two-step hydrothermal reaction at room temperature and one-step direct carbonization, which is facile, low-cost and environmentally friendly. It exhibits the desired overpotentials of 199 mV at 10 mA cm⁻² in an alkaline solution and 246 mV at 10 mA cm⁻² in an acidic solution. Besides, it has satisfactory durability, which is better than that of a commercial Pt/C catalyst.

2. Experimental section

2.1. Reagents

Potassium ferricyanide (K₃[Fe(CN)₆], analytical reagent), potassium ferrocyanide trihydrate (K₄[Fe(CN)₆]·3H₂O, analytical reagent), sodium citrate (Na₃C₆H₅O₇, 99%), ethyl alcohol (C₂H₅OH, ≥99.8%), sulfuric acid (H₂SO₄, 98%) and potassium hydroxide (KOH, 96%) were obtained from Beijing Chemical Works. Nickel nitrate hexahydrate (Ni(NO₃)₂·6H₂O, 98%) and ammonium molybdate tetrahydrate (H₂₄Mo₇N₆O₂₄·4H₂0) were obtained from Aladdin. Pt/C (20 wt%, JM), Nafion (5.0 wt%, Dupont), and N₂ gas (99.99%) were also employed. All chemical reagents were used as received without further purification. All aqueous solutions were prepared with ultrapure water (resistivity of 18.25 MΩ cm).

2.2. Physical characterization

Scanning electron microscopy (SEM) was performed on a HITACHI SU020 microscope. Transmission electron microscopy (TEM) and elemental mapping were performed on an FEI Tecnai G20/JEM2010 microscope. X-ray photoelectron spectra (XPS) were recorded on a Thermo ESCALAB 250Xi with an excitation source of Al Kα radiation. X-ray diffraction (XRD) patterns were carried out using an Empyrean (PANalytical B.V.) with a Cu Kα radiation source (λ₁ = 1.5406 Å) operating at 40.0 kV and 40.0 mA, and the diffraction data were recorded in the 2θ range of 5–80° with a scan rate of 4 degrees per min.

2.3. Preparation of Fe³⁺NiMoC

In a typical procedure,³⁰ 0.6 mmol of nickel nitrate and 0.9 mmol of sodium citrate were dissolved in 20 mL of deionized (DI) water to form solution A, and 0.4 mmol of potassium ferricyanide was dissolved in another 20 mL of DI water to form solution B. Solutions A and B were then mixed under stirring for 1 min. The obtained mixed solution was aged for 18 h at room temperature. The mixed solution was centrifuged and washed several times with DI water and dried in a vacuum overnight at 60 °C to obtain the Fe–Ni Prussian blue analogue (Fe³⁺Ni-PBA). In addition, 0.4 mmol of ferrocyanide trihydrate was used to take the place of 0.4 mmol of potassium ferricyanide and the product was named Fe²⁺Ni-PBA.

Next, 200 mg of Fe³⁺Ni-PBA was dissolved in 10 ml of DI water, which was subsequently injected into 10 ml of DI water containing 200 mg of ammonium molybdate tetrahydrate. The mixed solution was then stirred for 24 h at room temperature, centrifuged with DI water several times and dried overnight in a vacuum at 60 °C to get Fe, Ni and Mo compounds named Fe³⁺NiMo. In addition, Fe²⁺Ni-PBA was treated in the same way to get Fe²⁺NiMo. The precipitate (Fe²⁺NiMo or Fe³⁺NiMo) was heated at 800 °C for 4 h at a rate of 3 °C min⁻¹ in a tube furnace and in N₂ atmosphere to obtain the carbide of FeNiMo compounds. The final products were named Fe³⁺NiMoC or Fe²⁺NiMoC, respectively. As control groups, Fe²⁺Ni-PBA and Fe³⁺Ni-PBA were heated under the same conditions as above to get the corresponding carbonization products, which were named Fe²⁺Ni-PBAC and Fe³⁺Ni-PBAC, respectively.

2.4. Cathode preparation

Briefly, 5 mg of (Fe²⁺Ni-PBAC, Fe³⁺Ni-PBAC, Fe²⁺NiMoC, Fe³⁺NiMoC or Pt/C (20 wt%)) was dispersed in 240 μL of a mixed solution of ethyl alcohol, 240 μL of ultrapure water and 20 μL of 5 wt% Nafion and ultrasonicated for 10 min. Next, 5 μL of liquid was pipetted onto the surface of a glassy carbon electrode (GCE, 3 mm) (loading ∼0.7077 mg cm⁻²) and allowed to dry naturally. The modified GCE served as the working electrode.

2.5. Electrochemical measurements

Electrochemical measurements were performed using a CHI 660E electrochemical workstation with a three-electrode system that included a working electrode (GCE), a counter electrode (Pt foil, 1 × 1 cm²) and a reference electrode (Hg/HgO, 1 M KOH electrolyte) in 1 M KOH solution, or a Hg/Hg₂SO₄ (saturated K₂SO₄ electrolyte) electrode in 0.5 M H₂SO₄ solution. The experimental potential values were calibrated by using the following equation: E vs. RHE = E vs. Hg/HgO + 0.098 + 0.059 pH; E vs. RHE = E vs. Hg/Hg₂SO₄ + 0.616 + 0.059 pH. Before the test, N₂ flow (20 mL min⁻¹) was continuously fed to the cathode through the electrolyte in the cell for 30 min. The linear sweep voltammetry (LSV) experiments were performed at a scan rate of 10 mV s⁻¹ from 0.2 to −0.7 V (vs. RHE) in N₂-saturated 0.5 M H₂SO₄ or 1 M KOH solution, respectively. Electrochemical impedance spectra (EIS) measurements were performed at an overpotential of 300 mV (vs. RHE) with frequencies from 0.1 to 100 000 Hz and an amplitude of 5 mV. The electrochemically active surface area (ECSA) was estimated by CVs and was tested from −0.80 to −0.70 V (vs. Hg/HgO) with a scan rate from 10 to 100 mV s⁻¹ in N₂-saturated 1 M KOH, or tested from −0.65 to −0.55 V (vs. Hg/Hg₂SO₄) with a scan rate from 10 to 100 mV s⁻¹ in N₂-saturated 0.5 M H₂SO₄. Durability cyclic voltammetry (CV) tests were conducted from −0.4 to 0 V (vs. RHE) in N₂-saturated 0.5 M H₂SO₄ or 1 M KOH solution with the scan rate of 100 mV s⁻¹ for 10 000 segments and the differences in the LSV curves before and after CVs were compared.

3. Results and discussion

3.1 Physical characterization

SEM was used to observe the morphologies of the samples before carbonization. As shown in Fig. 1a and b, the Fe²⁺Ni-PBA has irregular aggregation while the Fe³⁺Ni-PBA is made of independent cubic nanocrystals. The addition of ammonium molybdate tetrahydrate made the Fe²⁺Ni-PBA particles stick together (Fig. 1c) while most of the Fe³⁺Ni-PBA cubes remained uniform and independent after mixing (Fig. 1d), which allowed them to form dispersive nanoparticles after carbonization (Fig. 2a), thus enlarging the surface area and increasing the number of active sites.

Fig. 1 SEM images of Fe²⁺Ni-PBA (a), Fe³⁺Ni-PBA (b), Fe²⁺NiMo (c), and Fe³⁺NiMo (d) before carbonization.

Fig. 2 TEM images (a–c) and the corresponding mapping images (d–i) of Fe³⁺NiMoC.

In Fig. 2a, the metallic nanoparticles are surrounded by graphitic layers that can serve as a “cage”, encapsulating the metallic compounds inside. These carbon cages are connected by carbonized tubes made from N-doped carbon (Fig. 2g and h).

In order to investigate the morphology of the single carbon cage, high-resolution TEM was carried out. In Fig. 2b, the Fe, Ni and Mo compounds, including Fe_0.64Ni_0.36, Mo₂C and MoO₃, are wrapped by the graphitic layers. The graphitic layers can serve as a carbon cage and encapsulate the Fe, Ni and Mo compounds inside, which can protect the active sites from the environment. The graphitic layers can also serve as a desirable electron transport medium due to its excellent conductivity. Thus, the graphitic layer structure can enhance the durability and improve the catalytic efficiency at the same time. Besides, the graphitic layers were not oriented parallel to the axis and showed considerable defects and edges on the surface,³¹ which can improve the surface affinity for H⁺ in the solution.

The XRD pattern of Fe³⁺NiMoC is shown in Fig. 3a. The typical peak at ≈25° indicates the (002) face of graphite carbon, which is characteristic of the carbon framework. The diffraction peaks at 43.6°, 50.8°, and 74.7° can be indexed to the (111), (200), and (220) planes of Fe_0.64Ni_0.36, and the peaks at 34.3°, 37.9°, 39.3°, 52.1°, 61.4°, 69.5°, 72.3°, 74.5° and 75.5° can be assigned to the (021), (200), (121), (221), (040), (321), (042), (240) and (142) planes of Mo₂C.³²

Fig. 3 XRD pattern (a), XPS survey spectrum (b) and the corresponding high-resolution spectra (c–h) of Fe³⁺NiMoC.

In order to investigate the compound surface including the chemical composition and element bonding configurations, X-ray photoelectron spectroscopy (XPS) was carried out for Fe³⁺NiMoC. As shown in Fig. 3b, the existence of C, N, O, Fe, Ni and Mo with the atomic contents of C-43.15%, N-22.47%, O-20.15%, Fe-3.75%, N-2.16% and Mo-8.32% was confirmed. In the C 1s spectra (Fig. 3c), the peaks were observed at 284.5, 285.5, and 286.5 eV, which can be ascribed to C=C, C–C and C–O, respectively.^33,34Fig. 3d shows the high-resolution spectrum of N 1s, which presents 4 types of N coordination environments at 398.6 eV for pyridinic-N, 400.3 eV for pyrrolic-N, 401.1 eV for graphitic-N and 402.7 eV for oxidized-N.^35,36 Meanwhile, the N content was determined to be 3.94 at%, which suggests that N atoms have been successfully doped into the carbon network. N doping in the porous carbon is beneficial for stabilizing metallic Fe, Ni and Mo as well as their compounds. In the meantime, it can regulate the electronic structure and surface permeability of catalyst.⁵ The O 1s spectrum in Fig. 3e contains three peaks at 530.4  eV, 531.0  eV and 532.1  eV belonging to lattice oxygen, –OH groups and adsorbed H₂O, respectively. These three peaks all shifted to high binding energies compared to pure MoO₃,³⁷ suggesting that electrons were transferred from the oxygen of MoO₃ to Ni, which decreased the electron cloud density of oxygen. Therefore, the binding energies changed and partial oxygen vacancies were formed.^38,39 In Fig. 3f and g, the Fe⁰2p and Ni⁰2p peaks can be ascribed to the Fe³⁺ and Ni²⁺ ions being reduced to Fe_0.64Ni_0.36 at high temperature. The Fe²⁺2p and Ni²⁺2p peaks may belong to the coordination center of N-doped carbon. In addition, the Fe and Ni satellite peaks can be ascribed to the formation of the iron carbide and the spinel structure NiFe₂O₄,^40,41 which were possibly produced by calcining the Fe³⁺, Ni²⁺ and sodium citrate at high temperatures and both have been reported to be excellent active centres toward the HER.³¹ In Fig. 3h, the Mo 3d peaks at 232.7  eV and 235.8  eV are assigned to Mo⁶⁺ 3d_5/2 and Mo⁶⁺ 3d_3/2 of MoO₃ produced by the thermal decomposition of ammonium molybdate.⁴² Mo⁵⁺ peaks (232.5 eV and 234.8 eV) reveal the formation of oxygen vacancies due to the substitution of Ni and Fe atoms for Mo atoms in MoO₃ lattice.⁴³

In the XRD patterns, Mo₂C has the highest content among the Mo compounds while XPS indicates that the oxide of Mo dominates. This is mostly because XRD studies the bulk phase while XPS focuses on the surface; i.e., Fe³⁺NiMoC is mainly made up of Fe₀₆₄Ni₀₃₆ and Mo₂C with the surface oxidation of Mo. In general, the N-doped carbon network established by carbonizing Fe³⁺Ni-PBA can serve as a conductive fundamental base to tightly immobilize carbon cages. The carbon cages can form a natural barrier to keep metallic active sites inside from being damaged by the environment. The low oxygen coordinated defect sites in the Fe, Ni and Mo compounds can serve as the HER active center, thus enhancing the electrocatalytic activity.^30,44,45

3.2 HER catalytic activities in acidic solution

The HER catalytic performance was firstly tested in 0.5 M H₂SO₄. As seen in Fig. 4a and b, Fe³⁺Ni-PBAC (471 mV vs. RHE) and Fe³⁺NiMoC (246 mV vs. RHE) showed lower overpotentials as compared to Fe²⁺Ni-PBAC (616 mV vs. RHE) and Fe²⁺NiMoC (393 mV vs. RHE) at 10 mA cm⁻², respectively, which suggests that the electrocatalysts synthesized by Fe³⁺ have better catalytic activity toward the HER. This is probably due to the uniform and independent catalytic units providing a larger surface area and more active sites. On the other hand, Fe²⁺NiMoC and Fe³⁺NiMoC showed lower overpotentials (393 mV and 246 mV vs. RHE) compared to the Fe²⁺Ni-PBAC and Fe³⁺Ni-PBAC (616 mV and 417 mV vs. RHE) at 10 mA cm⁻², respectively, which indicates that the addition of Mo and its compounds can enhance the catalytic efficiency toward the HER. This is consistent with the results of a previous report.⁴⁶ For comparison, the 20% Pt/C was tested in the same way and showed an overpotential of 42 mV (vs. RHE) (Fig. 3a).

Fig. 4 (a) iR-corrected LSV curves of Fe²⁺Ni-PBAC, Fe³⁺Ni-PBAC, Fe²⁺NiMoC, Fe³⁺NiMoC and 20% Pt/C; (b) the corresponding overpotentials at 10 mA cm⁻². (c) Tafel plots and (d) EIS spectra for the HER at −0.3 V (vs. RHE). The electrolyte solution was 0.5 M H₂SO₄.

To gain insight into the kinetics and mechanism for the HER, the Tafel plots derived from the corresponding polarization curves are presented in Fig. 4c. The Fe³⁺NiMoC displays a Tafel slope of −75.1 mV dec⁻¹ compared to Pt/C catalyst (−33.0 mV dec⁻¹). The Tafel slope is an intrinsic property of the electrocatalytic HER activity, which is related to the rate-determining step of the HER. A lower Tafel slope shows better HER kinetics.⁴⁷ In the aqueous electrolyte, H⁺ ions obtained electrons to form H atoms and were adsorbed on the surface of the working electrode (Volmer reaction, H₃O⁺ + e⁻ → H_ads),⁴⁸ followed by either an electrochemical desorption step (Heyrovsky reaction, H_ads + H₃O⁺ + e⁻ → H₂) or a chemical desorption step (H_ads + H_ads → H₂) to form hydrogen molecules.⁵ The theoretical Tafel slopes of the Volmer, Heyrovsky and Tafel reactions are −120, −40 and −30 mV dec⁻¹, respectively. The Tafel slope of the Fe³⁺NiMoC was −75.1 mV dec⁻¹, which is a Volmer–Heyrovsky mechanism with the Heyrovsky step is the rate-determining step.⁴⁸ In order to study the charge transfer resistances of these 4 samples, the electrochemical impedance spectra were employed. Fig. 4d is the EIS of Fe²⁺Ni-PBAC, Fe³⁺Ni-PBAC, Fe²⁺NiMoC and Fe³⁺NiMoC at −0.3 V (vs. RHE). The Fe³⁺NiMoC has the minimum charge transfer resistance and thus promotes the kinetics of the HER. Besides, the charge transfer resistances and Tafel slopes, Fe³⁺NiMoC < Fe²⁺NiMoC < Fe³⁺Ni-PBAC < Fe²⁺Ni-PBAC, which is consistent with the trend of the HER overpotentials mentioned above (Fig. 4a and b).

3.3 HER catalytic activities in alkaline solution

The HER catalytic performance was also tested in 1 M KOH. As shown in Fig. 5b and c, Fe³⁺NiMoC exhibits the smallest Tafel slope and overpotential (116.9 mV dec⁻¹, 199 mV) of all samples (Fe³⁺Ni-PBAC(133. 1 mV dec⁻¹, 298 mV), Fe²⁺NiMoC(135.2 mV dec⁻¹, 355 mV), Fe²⁺Ni-PBAC(209.7 mV dec⁻¹, 548 mV)) except for the commercial Pt/C catalyst (54.2 mV dec⁻¹, 43 mV), which suggests that the HER kinetics of Fe³⁺NiMoC is favorable and the current density of Fe³⁺NiMoC will increase faster as the potential becomes more negative. EIS spectra are also shown in Fig. 5d, illustrating that Fe³⁺NiMoC has the smallest intrinsic resistance and charge transfer resistance, which facilitates the kinetics towards the HER, too.

Fig. 5 iR-corrected LSV curves of Fe²⁺Ni-PBAC, Fe³⁺Ni-PBAC, Fe²⁺NiMoC, Fe³⁺NiMoC and 20% Pt/C (a); the corresponding overpotentials at 10 mA cm⁻² (b); Tafel plots (c) and EIS spectra for HER at −0.3 V (vs. RHE) (d). The electrolyte solution was 1 M KOH.

It is worth noting that in alkaline solution (1 M KOH), the order of catalytic efficiency is as follows: Fe³⁺NiMoC > Fe³⁺Ni-PBAC > Fe²⁺NiMoC > Fe²⁺Ni-PBAC. However, in acidic solution (0.5 M H₂SO₄), the order is Fe³⁺NiMoC > Fe²⁺NiMoC > Fe³⁺Ni-PBAC > Fe²⁺Ni-PBAC. In other words, the Fe³⁺Ni-PBAC shows a better catalytic effect in alkaline solution while the Fe²⁺NiMoC is better in the acidic solution. This is probably because in acidic solution, the desorption of H₂ (H_ads + H_ads → H₂) is the rate-determining step due to the abundant H⁺ environment, and the Fe²⁺NiMoC has a weaker adsorption capacity toward H_ads so it exhibits a better catalytic effect than Fe³⁺Ni-PBAC. When it comes to the alkaline solution, the adsorption of H⁺ (H₃O⁺ + e⁻ → H_ads) is the rate-determining step on account of the lack of H⁺. Therefore, the independent catalytic units and larger surface area led to Fe³⁺Ni-PBAC demonstrating preferable catalytic performance in alkaline solution.

3.4 Durability and activities of electrocatalyst

The ECSA was estimated by CVs with the equation ECSA = C_dl/C_s (where C_dl is the double layer capacitance, C_s is the capacitive behavior). The larger ECSA means more active sites.⁴⁹ Since the C_s of Fe³⁺NiMoC is unknown, we can estimate the ECSA by comparing the value of C_dl; C_dl can be calculated from the slope of the ΔJ-scan rate line.⁵⁰ The CV was firstly tested from −0.65 to −0.55 V (vs. Hg/Hg₂SO₄) with scan rates from 10 to 100 mV s⁻¹ in 0.5 M H₂SO₄ (Fig. 6a and b). C_dl was calculated with ΔJ − 0.60 V (vs. Hg/Hg₂SO₄). The value of C_dl (μF cm⁻²) is half of the slope,⁵¹ which is 12.9 μF cm⁻² for Fe³⁺NiMoC, 2.9 μF cm⁻² for Fe³⁺Ni-PBAC, 1.6 μF cm⁻² for Fe²⁺NiMoC and 0.5 μF cm⁻² for Fe²⁺Ni-PBAC. The CV was also tested from −0.90 to −0.80 V (vs. Hg/HgO) with a scan rate from 10 to 100 mV s⁻¹ in 1 M KOH (Fig. 6c and d). C_dl was calculated with ΔJ at −0.85 V (vs. Hg/HgO). The value of C_dl (μF cm⁻²) was 20.3 μF cm⁻² for Fe³⁺NiMoC, 4.6 μF cm⁻² for Fe³⁺Ni-PBAC, 4.6 μF cm⁻² for Fe²⁺NiMoC and 0.4 μF cm⁻² for Fe²⁺Ni-PBAC. It was assumed that the catalytic effect can be improved with the increasing quantity of catalytically active sites, which is consistent with the results of 3.2 and 3.3.

Fig. 6 C _dls was calculated with ΔJ at −0.60 V (vs. Hg/Hg₂SO₄) in 0.5 M H₂SO₄ (a) and the corresponding CV curves of Fe³⁺NiMoC (b). C_dls was calculated with ΔJ at −0.85 V (vs. Hg/HgO) in 1 M KOH (c) and the corresponding CV curves of Fe³⁺NiMoC (d). iR-corrected LSV curves of Fe³⁺NiMoC and Pt/C before and after 10 000 CVs in 0.5 M H₂SO₄ (e) and in 1 M KOH (f).

In order to investigate the durability of the catalyst, CVs were carried out in 0.5 M H₂SO₄ or 1 M KOH solution. Fe³⁺NiMoC and 20% commercial Pt/C were electrolyzed from −0.4 to 0 V (vs. RHE) in N₂-saturated 0.5 M H₂SO₄ or 1 M KOH solution with the scan rate of 100 mV s⁻¹ for 10 000 segments. In Fig. 6e and f, the LSV curves before and after CVs demonstrate that Fe³⁺NiMoC has less current density loss after CVs than commercial 20% Pt/C in 0.5 M H₂SO₄ or 1 M KOH, which suggests that Fe³⁺NiMoC is more durable compared to commercial Pt/C.

4. Conclusion

In summary, we synthesized a new carbon cage-encapsulated FeNiMo compound material to electrocatalyze the HER. This non-noble metal catalyst exhibits excellent electrocatalytic performance in both acidic (246 mV, 10 mA cm⁻²) and alkaline (199 mV, 10 mA cm⁻²) solutions. More importantly, we have found a cheap and feasible way to establish a carbon cage structure, which can further enhance the durability of the non-metal catalyst. In general, this paper provides a promising way to decrease the cost of the catalyst for the HER by using an efficient and durable non-noble metal catalyst to replace the noble-metal one.

Conflicts of interest

The authors have no competing interests to declare.

Acknowledgements

This work was supported by National Key R&D Program of China (No. 2016YFC1102802).

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Footnote

† Electronic supplementary information (ESI) available. See DOI: 10.1039/d0ma00065e

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