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A POMOFs-Derived FeP/MoP Hybrid Encapsulated in N/P DualDoped Carbon as Efficient Electrocatalyst for Hydrogen Evolution Ji-Sen Li, Shuai Zhang, Jing-Quan Sha, Jia-Yi Li, Xiao-Rong Wang, and Hao Wang Cryst. Growth Des., Just Accepted Manuscript • DOI: 10.1021/acs.cgd.8b00766 • Publication Date (Web): 27 Jun 2018 Downloaded from http://pubs.acs.org on June 28, 2018

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Crystal Growth & Design

A POMOFs-Derived FeP/MoP Hybrid Encapsulated in N/P Dual-Doped Carbon as Efficient Electrocatalyst for Hydrogen Evolution Ji-Sen Li*†, Shuai Zhang†, Jing-Quan Sha†, Jia-Yi Li†, Xiao-Rong Wang†, and Hao Wang† †

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

and Chemical Engineering, Jining University, Qufu, Shandong 273155, P. R. China

ABSTRACT: The design and fabrication of noble-free metal electrocatalysts for efficient hydrogen production with long-term stability are of great significance, but very challenging. Herein, for the first time, we report an iron phosphide/molybdenum phosphide hybrid covered by nitrogen/phosphorus dual-doped carbon (FeP/MoP@NPC) using POMOFs as templates by a facile two-step approach. As expected, the composite shows highly efficient electrocatalytic performance toward the hydrogen evolution reaction with a low onset overpotential (76 mV), small Tafel slope (56.5 mV dec-1), and excellent catalytic stability for 10 h owing to its distinct nanostructure and strong synergistic effect of FeP and MoP. More importantly, this work offers a novel methodology for exploiting transition-metal-based electrocatalysts for clean and renewable energy technology.

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KEYWORDS: bimetallic phosphides, electrocatalyst, hydrogen evolution reaction, heteroatomdoped carbon, metal-organic frameworks

Hydrogen, as a promising alternative to carbon-based fuels, has attracted extensive attention due to its sustainable and renewable properties. Water splitting is recognized as an appealing approach for high-purity hydrogen production, however, a high-performance and long-term stable electrocatalyst is of urgency to lower the overpotentials.1, 2 As is well-known, platinum (Pt) is believed to be the best electrocatalyst for hydrogen evolution reaction (HER), but the relative rarity and high cost significantly limit scalable industrial applications.3-5 Therefore, design and exploration of earth-abundance and efficient electrocatalysts as the replacement of Pt is highly desirable for fulfilling the hydrogen economy. In recent years, transition metal phosphides (TMPs) as potential substitutes of noble-metal catalysts have captured tremendous interest due to their high catalytic performances and hydrogenase-like catalytic mechanism for HER.6, 7 For instance, Fe,8-11 Co,12-15 Ni,16-18 Cu,19, 20 Mo,21,

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and W23,

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based TMPs have been employed as efficient HER electrocatalysts.

Regretfully, few of them show satisfying expectations in comparison to noble-metal catalysts. As a consequence, to further boost their electrochemical activities, bimetallic phosphides are expected to be constructed because the introduction of secondary metal into TMPs contributes to tune the intrinsic electric structures of hybrids and regulate the surface properties of hybrid materials to expose a lot of active sites.25-31 On the other hand, TMPs anchored into carbon-based nanomaterials have been proven to be an effective strategy to accelerate electron-transfer rates and improve their durability.32, 33 Despite great progress, it still remains a significant challenge to


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develop bimetallic phosphides-based catalysts with superior catalytic performance and stability toward HER through a facile synthesis procedure. Metal-organic frameworks (MOFs) composed of inorganic metal nodes and organic ligands have become one of the hottest subjects due to larger surface area and versatile functionalities.34, 35

Especially, MOFs-derived nanomaterials have shown promising potential for electrocatalysis

applications.36-41 Nevertheless, MOFs-assisted approaches are mainly employed to fabricate monometallic phosphide,42-44 and few papers have been reported on MOFs-based bimetallic phosphides.45-49 In particular, introducing early-transition metal to synthesize bimetallic phosphides based catalysts derived from MOFs are rarely investigated, which are difficult to obtain by the direct pyrolysis of single MOFs. Fortunately, as a class of MOFs, polyoxometalatebased MOFs (POMOFs) possessing the merits of POMs and MOFs can serve as both earlytransition metals (Mo, W, and V) and carbon sources simultaneously, which can be considered as ideal precursors to synthesize Mo, W, and V-containing materials.50-52 To our knowledge, the design and development of carbon-supported early transition-metal-based bimetallic phosphides derived from POMOFs has not been reported so far. Motivated by above-mentioned, we have innovatively conceived a new strategy to synthesize a new bimetallic-structured phosphide electrocatalyst consisting of FeP/MoP nanoparticles (NPs) encapsulated into N/P dual-doped carbon (denoted as FeP/MoP@NPC) using PMo12@MIL-100 as precursor. Benefitting from the ingenious design, the excellent synergistic effect of components and heteroatoms dual-doped carbon could be achieved at the same time. Impressively, the composite shows outstanding catalytic performance and good cycling stability for the HER, which outperforms those of FeP@NPC. As far as we know, this is the first report of POMOFs-derived Mo-containing bimetallic phosphide catalysts with high HER catalytic activity.


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Scheme 1. Schematic diagram for the formation of FeP/MoP@NPC through carbonization and subsequent phosphidation process. Red and green spheres represent FeP and MoP NPs. The FeP/MoP@NPC composite was synthesized through a facile two-step heat-treatment (Scheme 1) of a mixture of PMo12@MIL-100 (Figure S1) and melamine. In brief, the mixture was firstly carbonized at 600 oC under Ar atmosphere. And then, the resultant sample was reduced into FeP/MoP@NPC at 850 oC by PH3 which results from the decomposition of (NH4)2HPO4. Notably, in this synthetic process, melamine not only offers carbon and nitrogen sources, but facilitates the in situ production of N/P dual-doped carbon layers coating FeP/MoP NPs, which contribute to a significant improvement in the stability of FeP/MoP@NPC.


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Figure 1. (a) SEM, (b) TEM, (c) HRTEM, (d) elemental mapping images, and (e) EDS spectrum of FeP/MoP@NPC. Figure 1a, b show the scanning electron microscopy (SEM) and transmission electron microscopy (TEM) images of FeP/MoP@NPC, which confirm that the as-synthesized nanostructure consists of FeP/MoP NPs and N/P dual-doped carbon. High-resolution transmission electron microscopy (HRTEM) image in Figure 1c exhibits the FeP/MoP NPs are well coated by carbon layers with a lattice spacing of 0.34 nm, which can not only prevent the central NPs from corrosion but also promote the charge transfer process.32, 42 In addition, the well-defined fringe spacings can be distinctly observed in the HRTEM images, where the 0.27 nm corresponds to the (011) lattice plane of FeP, and the 0.32 nm belongs to (001) plane of MoP. The elemental mapping in Figure 1d shows that Fe, Mo, P, N, and C elements are uniformly distributed throughout the hybrid, which is consistent with the analysis of energy dispersive spectrometer (EDS) spectrum (Figure 1e).


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Figure 2. (a) PXRD pattern and (b) Raman spectrum of FeP/MoP@NPC. X-ray diffraction (XRD) was adopted to characterize phase nature of the FeP/MoP@NPC. As displayed in Figure 2a, the main peaks located at 30.8, 32.8, 34.5, 35.5, 37.2, 45.6, 47.1, 48.3, 50.4, 55.3, 56.1, 59.6, and 79.2o are assignable to the (002), (011), (220), (102), (111), (210), (202), (211), (103), (301), (013), (020), and (222) facets of orthorhombic FeP (JCPDS, No, 652595), respectively. The other obvious peaks can be assigned to the crystallized MoP phase (JCPDS, No, 65-6487). On the contrary, the weak diffraction peak (≈23o) is attributed to the (002) plane of carbon. In addition, the degree of graphitization was also analyzed from Raman spectroscopy, illustrated in Figure 2b. In comparison with that of FeP@NPC (0.58) in Figure S2f, the integral area ratio of G (1598.9 cm-1) and D (1356.8 cm-1) bands is 0.68 for FeP/MoP@NPC, implying the good graphitic structure, which is favorable for improving HER activity.50


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Figure 3. (a) XPS survey spectrum, (b) C 1s, (c) N 1s, (d) Fe 2p, (e) Mo 3d, and (f) P 2p in FeP/MoP@NPC. The survey spectrum of FeP/MoP@NPC in Figure 3a demonstrates that the catalyst surface consists of P, C, N, Mo, O, and Fe components. The element O could originate from surface oxidation of FeP/MoP due to air contact. Meanwhile, Table S1 lists the corresponding element content. From C1s XPS spectrum (Figure 3b), it is found that a strong peak of C=C/C-C is located at 284.4 eV, and the other relatively weak peaks at 285.1, 286.3, and 289.2 eV are attributed to C-P, C-N, and O-C=O bonds,3,

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which validates N and P dual-doping. The

deconvoluted N 1s spectrum (Figure 3c) confirms the existence of graphitic N (401.5 eV), pyrrolic N (399.7 eV), and pyridinic N (398.3 eV).12, 50, 52 In terms of Fe 2p, the peaks centered at 707.9 and 720.1 eV (Figure 3d) are assignable to Fe 2p3/2 and Fe 2p1/2, signifying the existence of Fe3+. The binding energies at 712.9 and 726.6 eV correspond to high oxidation state of Fe


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species.8, 10 Figure 3e exhibits three doublets: at 231.7/232.9 eV and 233.5/236.3 eV (Mo-Ox) coming from partially oxidized Mo species, 228.4/232.2 eV corresponding to MoP.21, 41, 52 The P 2p region (Figure 2f) exhibits four peaks, where the bind energies at 129.7 and 130.4 eV can be ascribed to P 2p3/2 and P 2p1/2.10,

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The rest of two sharp peaks at 133.5 and 134.3 eV is

representative of P-C and P-O owing to the contamination of the sample surface. In particular, it should be noted that the electron binding energies of Fe 2p and Mo 3d have the positive shift of about 1.1 and 0.8 eV compared to that of metallic Fe and Mo, whereas the binding energy of P 2p reveals a negative shift of 0.8 eV in contrast to that of elemental P0, meaning that electron transfer proceeds from Fe/Mo to P.18 This result significantly verifies that both Fe/Mo (δ+) and basic P (δ-) can be regarded as catalytic sites for the hydrogen production. That is, both Fe and Mo centers serve as the hydride-acceptor centers. The P centers function as the proton-acceptor centers, which could simultaneously promote the generation of Fe/Mo-hydride for following hydrogen evolution through electrochemical desorption.8,

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As control experiment, the

FeP@NPC hybrid was also characterized in details (Figure S2-3).

Figure 4. (a) Polarization curves. (b) Tafel plots. (c) Capacitive current at -9 mV at different scan rates of FeP/MoP@NPC and FeP@NPC. (d) Current-time (i-t) curve of FeP/MoP@NPC at


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10 mA cm-2 for 10 h. Inset: polarization curves of FeP/MoP@NPC at 100 mV s-1 before and after 1000 cycles. The electrocatalytic properties of FeP/MoP@NPC toward the HER were examined utilizing a three-electrode cell. Herein, polarization curves were presented and not corrected for iR loss. In order to optimize experiment conditions, the influences of carbonization and phosphidation temperature on the HER activity have been pre-investigated, respectively. A series of samples obtained at various carbonization (500, 600, and 700 oC) and phosphidation temperatures (750, 850, and 950 oC) were evaluated and the corresponding characterizations were shown in Figure S4-5. On the basis of linear sweep voltammetry (LSV) and Tafel slope (Figure S6-7), the best performances were acquired at 600 and 850 oC, respectively, suggesting that they are the optimal carbonization and phosphidation temperature. LSVs in Figure 4a demonstrate that the FeP/MoP@NPC hybrid shows an onset overpotential (~76 mV), which is superior to that on FeP@NPC (~118 mV). The electron-transfer kinetics of HER over the as-prepared catalysts were assessed by analyzing Tafel plots. Compared to FeP@NPC (72.2 mV dec-1), the Tafel slope of FeP/MoP@NPC is 56.5 mV dec-1 (Figure 4b), slightly higher than that of commercial Pt-C (30 mV dec-1). This indicates a Volmer-Heyrovsky mechanism for the HER on the FeP/[email protected], 8, 42

To the best of our knowledge, the value is comparable with most of recently reported

prominent non-noble metal-based HER catalysts (Table S2). The double-layer capacitance (Cdl) at the solid-liquid interface was measured further to evaluate the electrochemically active surface area. As indicated in Figure 4c, compared to FeP@NPC (2.32 mF cm-2), the FeP/MoP@NPC shows the larger Cdl of 10.8 mF cm-2, which supports that the hybrid has more exposed active sites and large effective electrochemical surface area.


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For practical application, the stability of the catalyst is an important parameter. To probe the durability of FeP/MoP@NPC, chronoamperometry measure was carried out at 10 mA cm-2 (Figure 4d). Surprisingly, the electrocatalytic performace can be remained for 10 h with a current density of 84%. Moreover, continuous cyclic voltammetrys were also tests from -300 to 300 mV under a 100 mV s-1 scan rate. As shown in the inset of Figure 4d, the current densitypotential curve of FeP/MoP@NPC maintains negligible changes even after 1000 cycles. The TEM image and PXRD pattern of FeP/MoP@NPC after 1000 cycles are described in Figure S8. All results strongly prove the excellent stability of FeP/MoP@NPC, which may be related with the unique nanostructure. That is, the existence of carbon layers can significantly protect FeP/MoP NPs from agglomeration, corrosion and detachment, which is favorable for the enhancement of long-term stability. Considering the above results, the outstanding HER activity may result from the following factors: (i) generally, MoP and FeP crystalline phases possess high catalytic performances toward HER due to their excellent electrical conductivity and metalloid characteristics;8, 10, 42 (ii) because of the existence of carbon layer, the contact electrical resistance is effectively decreased and electron transport from central NPs to the electrodes is promoted.3, 44 As well, the corrosion and detachment of FeP/MoP@NPC are significantly prevented, further boosting its stability;13, 32 (iii) the introduction of the heteroatoms (N, P) is advantageous to the generation of more active sites.5, 19, 52 In summary, we have constructed a high efficient and robust FeP/MoP@NPC electrocatalyst derived from PMo12@MIL-100 by carbonization and subsequent phosphidation process. Remarkably, because of the synergetic contribution of FeP/MoP and NPC, the as-prepared composite possesses superior electroactivity and excellent long-term operation durability toward


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the HER, which is comparable to the high-efficiency transition-metal-based HER catalysts reported to date. This work not only offers a high active electrocatalyst toward HER, but provides an opportunity to design efficient and durable multi-metal phosphide based catalysts for energy conversion fields.

ASSOCIATED CONTENT Supporting Information. The Supporting Information is available free of charge on the ACS Publications website at DOI: xxxxxxxx. Experimental details, Figure S1-S8, and Tables S1-S2. AUTHOR INFORMATION Corresponding Author *E-mail: [email protected] ORCID Ji-Sen Li: 0000-0003-2578-422X Jing-Quan Sha: 0000-0002-5925-9565 Notes The authors declare no competing financial interest. ACKNOWLEDGMENTs


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Financial support from the Project of Shandong Province Higher Educational Science and Technology Program (J16LC02) and Talent Culturing Plan for Leading Disciplines of University in Shandong Province is gratefully acknowledged. REFERENCES (1) Dresselhaus, M. S.; Thomas, I. L. Alternative Energy Technologies. Nature 2001, 414, 332337. (2) Turner, J. A. Sustainable Hydrogen Production. Science 2004, 305, 972-974. (3) Li, J.-S.; Wang, Y.; Liu, C.-H.; Li, S.-L.; Wang, Y.-G.; Dong, L.-Z.; Dai, Z.-H.; Li, Y.-F.; Lan, Y.-Q. Coupled Molybdenum Carbide and Reduced Graphene Oxide Electrocatalysts for Efficient Hydrogen Evolution. Nat. Commun. 2016, 7, 11204. (4) Zhang, J.; Wang, T.; Liu, P.; Liao, Z.; Liu, S.; Zhuang, X.; Chen, M.; Zschech, E.; Feng, X. Efficient Hydrogen Production on MoNi4 Electrocatalysts with Fast Water Dissociation Kinetics. Nat. Commun. 2017, 8, 15437. (5) Jia, J.; Xiong, T.; Zhao, L.; Wang, F.; Liu, H.; Hu, R.; Zhou, J.; Zhou, W.; Chen, S. Ultrathin N-Doped Mo2C Nanosheets with Exposed Active Sites as Efficient Electrocatalyst for Hydrogen Evolution Reactions. ACS Nano 2017, 11, 12509-12518. (6) Wang, Y.; Kong, B.; Zhao, D.; Wang, H.; Selomulya, C. Strategies for Developing Transition Metal Phosphides as Heterogeneous Electrocatalysts for Water Splitting. Nano Today 2017, 15, 26-55.


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For Table of Contents Use Only

A POMOFs-Derived FeP/MoP Hybrid Encapsulated in N/P DualDoped Carbon as Efficient Electrocatalyst for Hydrogen Evolution Ji-Sen Li*, Shuai Zhang, Jing-Quan Sha, Jia-Yi Li, Xiao-Rong Wang, and Hao Wang

Table of Contents graphics and synopsis:

A FeP/MoP@NPC composite derived from POMOFs has been synthesized by a facile method for the first time, which shows highly efficient electrocatalytic activity for the HER.


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P Dual

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