Active and Durable Hydrogen Evolution Reaction Catalyst Derived

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An active and durable hydrogen evolution reaction catalyst derived from Pd-doped Metal-Organic Frameworks Jitang Chen, Guoliang Xia, Peng Jiang, Yang Yang, Ren Li, Ruohong Shi, Jianwei Su, and Qianwang Chen ACS Appl. Mater. Interfaces, Just Accepted Manuscript • DOI: 10.1021/acsami.6b01266 • Publication Date (Web): 26 Apr 2016 Downloaded from http://pubs.acs.org on April 29, 2016

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ACS Applied Materials & Interfaces

An active and durable hydrogen evolution reaction catalyst derived from Pd-doped Metal-Organic Frameworks Jitang Chen1, Guoliang Xia1, Peng Jiang1, Yang Yang1, Ren Li1, Ruohong Shi1, Jianwei Su1& Qianwang Chen1,2*

1 Hefei National Laboratory for Physical Science at Microscale, Department of Materials Science & Engineering & Collaborative InnovationCenter of Suzhou Nano Science and Technology, University of Science and Technology of China, Hefei 230026, China. 2 High Magnetic Field Laboratory, Hefei Institutes of Physical Science, Chinese Academy of Sciences, Hefei 230031, China. *Correspondence and requests for materials should be addressed to Q.C.(email: [email protected]).

Abstract The water electrolysis is of critical importance for sustainable hydrogen production. In this work, a highly efficient and stable PdCo alloy catalyst (PdCo@CN) was synthesized by direct annealing of Pd-doped MOFs under N2 atmosphere. In 0.5 M H2SO4 solution, PdCo@CN displays remarkable electrocatalytic performance with overpotential of 80 mV, a Tafel slope of 31 mV dec−1 and excellent stability of 10000 cycles. Our studies reveal that noble metal doped MOFs are ideal precursors for preparing highly active alloy electrocatalysts with low content of noble metal.

1. INTRODUCTION Nowadays and in the coming years, increasing attention is being paid to the development of sustainable and clean energy. Hydrogen (H2), a highly efficient and environmental friendly energy has drawn much attention, which can be produced by electrocatalytic water splitting.

1-5

Nevertheless, the water couldn’t be decomposed until the voltage increases to a certain value to overcome the thermodynamic equilibrium potential, which is known as the overpotential (η). Particularly, previous studies have shown that electrocatalysts can reduce the overpotential of the decomposition reactions.

3, 6-9

In the past decades, plenty of catalysts have been synthesized and

reported. Among them, the Pt catalyst is the best candidate for HER reaction, owing to its low overpotential and stability.

10-11

However, the abundance of Pt in the crust is 0.005ppm and the

price of Pt is ＄997 per ounce on the market, which limits its widespread application.12 Therefore,

ACS Paragon Plus Environment


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exploring inexpensive alternatives to platinum electrocatalysts still remains a major challenge. Among those alternatives, 3d transition metal based materials have received much research interests due to their high abundance and low price.

9, 13-16

However, the performances of these

catalysts are still unsatisfactory for their much higher overpotential compared to the noble metal based electrocatalysts. Previous studies showed that the formation of alloys would lead to a shift of charge distributions, resulting in the modification of the surface properties and the enhancement of the electrocatalystic characteristics.

2, 16-22

Hence, the performance and consumption might be

well balanced by alloying noble metal with transition metals. Pd is well-known for its high affinity for hydrogen, which facilitates the broad usage of Pd nanomaterials as primary catalysts, encompassing a wide variety of applications, particularly in electrocatalytic reaction.12, 23-26 Pd is regarded as a cheap alternative to the Pt as electrocatalysts because of its higher electrocatalytic activity and stability than those of 3d transition metals and their alloys. On the other hand, the electrolytes are often corrosive for the HER process. Thus, the stability of the catalysts should be taken into consideration. A corrosive resistant and electronically conductive shell is favorable to a metal or metal alloy electrocatalyst. Tremendous studies have been performed with various substrates wrap metals or alloys as model systems applied in electrochemical reactions.

13, 16-17, 20, 26-29

Nonetheless, many of these materials have complex

synthesizing procedures. As a result, a relatively simple and effective process in approaching uniform distribution alloys encapsulated in cage is of significant importance. In the past few years, metal-organic frameworks (MOFs) show broad and comprehensive applications as platforms to fabricate nanostructured materials, particularly composite materials, which can be applied in energy storage and conversion domains.

4-5, 16, 30-33

Prussian blue

analogues (PBA), as familiar MOFs, are often used as precursors to prepare metals, alloys and metallic oxides. 16, 30-31, 34 Herein, we report a simple and facile strategy to synthesize PdCo alloy wrapped in nitrogen-doped carbon (PdCo@CN) by annealing Pd-doped MOFs under N2 atmosphere, which presented excellent HER activity and long-term stability in acidic solution. The overpotential at current density of 10 mA cm-2 is only 80 mV (vs RHE), and the Tafel slope is 31 mV dec-1. To the best of our knowledge, this is the first report of noble metal doped MOFs-derived electrocatalyst for hydrogen evolution reaction.


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2. RESULTS AND DISCUSSION The synthesis process for the CoPd@NC hybrid was illustrated in Scheme 1. The preparation of Co3[Co(CN)6] and PdxCo3-x[Co(CN)6]2 was carried at room temperature, according to our previous works with a minor modification (detailed information is in the Supporting Information, SI). The final products were obtained after the precursors being annealed under nitrogen atmosphere. The sample prepared from nominal composition Pd：Co molar ratio of 1:6 was named as S-6. Similar structures have also been obtained with the same annealing strategy for reference compounds S-8, S-10 and S-0 (S-0 was derived from MOFs without noble metal doped).

Scheme 1 The synthetic route for PdCo alloy wrapped in nitrogen doped graphene shell. The typical XRD patterns of precursors were shown in Figure 1a. The diffraction peaks of the precursors could be indexed as (220), (400), (420), (422), (440), (600), (620), (640), and (642) reflections, which are consistent with the values for Co3[Co(CN)6]2·nH2O (JCPDS No. 77-1161). The strong and sharp reflection peaks and the smooth baseline indicated that the undoped sample was well crystallized. The XRD patterns of Pd-doped MOF show minor changes and the intensities of the weak peaks are related to Pd doping. As shown in Figure. 1b, XRD patterns of S-0 showed that no other impurity was presented in the sample except for the Co nanoparticles. Similar XRD patterns were also observed for hybrid compounds S-6, S-8 and S-10. The diffraction peaks occurring at 2θ=41.7°,44.7°,47.6°and 75.8° are characteristic of hexagonal Co lattices, which are indexed to the (100), (002), (101), and (110) crystalline planes of the hexagonal



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structure Co (JCPDS:05-0727). Raman spectroscopy has also been performed to determine the structural features of the carbonized sample (Figure. 1c. and Figure S3). As one can see that, the high ID/IG band intensity ratio and weak 2D band is the representative character of defect-rich and multilayer graphene, respectively. 16, 32, 35-36 The valence state of the components on the catalyst surface was identified by X-ray photoelectron spectroscopy (XPS) with survey (Figure S4) and peak deconvolution (Figure 1d-f). As shown in figure 1d, XPS investigation of the Co 2p spectrum revealed the presence of two chemically distinct species: metallic Co and Co(II) species peaks, which indicated the existence of trace of Co(II) originated from surface oxidation of metallic Co. The existence of Pd was confirmed by XPS (Figure 1e); Pd 3d peak could be deconvoluted into two pairs of doublets, and both of them were slightly shifted. 29, 37 The asymmetric N 1s XPS peak (Figure 1f) was deconvoluted into three peaks (398.6, 399.6 and 401.2 eV), and the percentage of the three peaks were 46.99%, 34.80% and 18.21%, respectively. Obviously, the peaks at 398.6 eV and 401.2 eV were corresponding to the presence of pyridinic N and quaternary N atoms. The shift of binding energy for Pd and Co revealed that there was interaction between the metals atoms and N atoms, verified by the appearance of the peak at 399.6 eV.

16, 20, 23, 27, 38

29, 38

which was

Owing to these interactions, the

electric charge distribution was changed, and the surface properties of metal NPs were mediated. 17, 39

The porosity of S-6, S-8 and S-10 were measured by N2 adsorption−desorption isotherms which were shown in Figure S5. All adsorption−desorption isotherms displayed type IV (based on IUPAC classification) isotherms with a hysteresis cycle, which indicate the presence of mesopores. The specific surface areas of S-6, S-8 and S-10 were 57.13, 36.05, and 29.89 m2 g−1, respectively. As the composites were derived from MOFs, the porous characteristics of MOFs play a crucial role in determining the pore texture of the resultant porous hybrids. For all samples, they derived from the analogous precursors, with different nominal compositions of Pd. The difference in the porosities might be attributed to the partially destroyed precursors’ frameworks during heterogeneous atoms doping. 35


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Figure 1 The XRD patterns of the precursors (a) and the final samples (b) (S-0, S-6, S-8, S-10); Raman spectra of S-6 (c); XPS spectra of S-6 (d)-(f) (Co-in-S-6 (d), Pd-in-S-6 (e), N-in-S-6 (f)). The SEM and TEM (Figure 2a, S1 and S2) images clearly revealed that both the noble metal doped MOFs and the undoped MOFs were cubic with a smooth surface. Once annealed in nitrogen atmosphere the regular cubic were collapsed into irregular nanoparticles (Figure 2b and S2). The TEM images (Figure 2c) illustrated that the irregular nanocomposites were composed of small encapsulated alloy particles. Further HRTEM analysis confirmed that the nanocomopsites were consisted of metal nanoparticles which were completely encapsulated by carbon cages with about 10 layers graphene (Figure 2d). The lattice fringes could be clearly seen in the HRTEM images, in which the 2.04 Å might be assigned to the (002) inter plane space of CoPd alloy, and the 3.4 Å belongs to (002) plane of graphene (Figure 2d). As shown in Figure 2 and Figure S6, the images of elemental mapping EDS line scan revealed that Pd and Co atoms were distributed across the nanoparticles uniformly, suggesting generated Pd-Co alloy.



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Figure 2 SEM images of precursor (a); S-6 (b); TEM image of S-6 (c); HRTEM of the S-6 (d); TEM image of the PdCo nanocrystal (e); elemental mappings of Pd (f); Co (g). The electrocatalytic HER capability of the catalysts was studied by steady-state linear sweep voltammetry (LSV) on glassy carbon electrode (GCE) in N2-saturated 0.5 M H2SO4 (SI). The polarization curves of samples were illustrated in Figure 3a. It was shown that, though inferior to the samples of alloy, the undoped catalyst exhibited a passable HER activity. These findings revealed that our three synthesized nanocomposites were effective catalysts for the HER. And the activity of the catalysts was in good agreement with Pd nominal compositions. To achieve a 10 mAcm-2 HER current density, the S-6, S-8 and S-10 require small overpotential of 80 mV, 85 mV and 100 mV, respectively, which is much lower than that of nondoped Co@NC (260 mV). Furthermore, our alloy catalysts show overwhelming performance compared with alloys between transition metals (shown in Table S1). We also compared our material with some palladium based catalysts (shown in Table 1). From the table, it was found that the catalyst shows comparable performance with a small overpotential, low


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Tafel slope. Moreover, the proportion of Pd in our catalyst was the lowest one in the table. From the results, we can draw a conclusion that annealing Pd-doped MOFs is a viable way to prepare robust alloy catalyst with a spot of noble metal. The HER performance of catalysts in an N2-saturated basic media was also investigated (1 M KOH). As shown in Figure S8, PdCo@CN also exhibited a high activity for HER in basic media, polarization curves of PdCo@CN showed an overpotential about 250 mV (vs RHE) at current density of 10 mA cm−2, this value is comparable with the most active non-noble metal HER 9, 28

electrocatalysts in basic solution, such as transition metal nanoparticle-based catalysts molybdenum carbide.

40

and

The result from ECSA provided the best agreement between the

information of the polarization curves (SI). The sample with a nominal starting molar Pd:Co ratio of 1:4 was (named as S-4) prepared and evaluated for its catalytic activity. The polarization curves of S-6 and S-4 in acidic solution were shown in Figure S9, which reveals that the performance of S-4 was slightly decreased. It is suggested that the catalyst shows the best performance at a moderate ratio of Pd.

19-20

Further

increasing the amount of Pd will lead to the formation of Pd-MOFs hybrid nanoparticles (Figure S10) instated of Pd-doped MOFs.

Table 1 Pd based catalysts for HER in acid media. Catalyst

Loading

Overpotential at

Tafel

Pd/M

Overpotential at

Reference

10 mA cm-2 (mV) amount (mg

10 mA cm-2 (mV)

cm-2)

slope

Molar

after certain

(mV

ratio

cycles

136

1/1

NA

41

47

23/77

About 90,

20

dec-1) Au-Pd-MWCCEa

3 mAcm-2

NA

at 300 mV (0.1M HCl) Au–Pd/CFP

a

0.5

About 90

1000th Pd/HOPG b

NA

About 150

118.3

/

NA

25

Pd

0.14

108 mA cm-2

34

/

108 mA cm-2 at

42

cube/PEI-rGO50:1c CoPd@NCa

at 100 mV 0.285

80

100 mV,1000th 31

1/15.8

67,10000th

This work

Notes: a. the value was estimated from EDX; b. Pd/HOPG was obtained by depositing Pd on Highly oriented pyrolytic graphite (HOPG), the content of Pd is



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unknown; c. Pd cube/PEI-rGO50:1 was obtained by immobilizing the Pd NCs onto PEI-rGO50:1 support and the content of Pd is 10 wt. % identified by AAS. d. Partial information was approximated from data graphs because it was not detailedly discussed in the literature.

To investigate the kinetics of HER process promoted by as-prepared catalysts Tafel plots analysis were carried out. As we know, discharge step, electrochemical desorption step and combination step of adsorbed hydrogen are three major reaction steps for HER in acid solutions. The present study showed that S-6 gives a Tafel slope of 31 mV dec−1, lower than that of S-8 (52 mV dec−1) and S-10 (71 mV dec−1) (Figure 3b). As the rate determining step (RDS) is reflected by the Tafel slope of a catalyst, the variation of Tafel slope can be explained by the change of RDS in HER process. The RDS for S-6 followed the Heyrovsky step, but for S-10 and S-8, the Volmer− Heyrovsky mechanism can be determined. Except for overpotential, durability is an important parameter in the exploration of electrocatalyst.17, 35, 43 To evaluate the durability of S-6 in acidic media, cycling test was applied with polarization curves at an accelerated scanning rate. There was a visible increase emerging after 1000 cycles, and no decrease observed in HER activity even after 10000 cycles in acidic environment, displaying an excellent durability (Figure 3c). Additionally, as illustrated in Figure 3d, the stable current density over 10 h of continuous operation at an applied overpotential of 0.1 V in an acidic media was presented, the current density showed an obvious increase from 20 mA cm−2 (at 0 s) to 36 mA cm−2 (at 10000 s), and it remained almost steady for 30000s. The enhanced electrocatalytic performance of the sample in cycling test and chronoamperometric scans is probably due to structure changing of the PdCo alloy. Elemental mapping, EDS line scan analysis and HRTEM were performed to survey the structure of the catalyst after HER. EDS scan line shows that the Pd content on the surface of PdCo alloy particles has been increased after hydrogen evolution reaction, which might be ascribed to the change of atmosphere. Previous study found that the element distribution within the shell of Rh0.5Pd0.5 NPs was depended on the surrounding atmosphere, where Pd would migrate to the shell, Rh migrate to the core in a reducing atmosphere.

44

Hydrogen emerged and bubbled from the surface of cathode during

catalytic reaction was proceeding. Then, the restructuring of the nanoparticles took place in the reducing atmosphere, where Pd migrated to outside layer of the alloy particles and enhanced the catalytic performance.


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The stability of the catalyst might be attributed the carbon shell of the alloy, which offered a reliable protection for the core.

16, 45

Additionally, The N doped carbon shell acted as a

multifunctional role. Firstly, the graphene layers served as fine conductor, which could boost the charge transfer effectively.16,

32

Secondly, because of the doped-heteroatom, carbon shell

contributes to the increased active sites and promoted HER performance.

35

All of above are

beneficial to the enhancement of HER performance.

Figure 3 The polarization curves of samples (a); Tafel plots of S-6, S-8 and S-10 (b); Polarization curves of S-6 after 1st, 1000th, 10000th cycles (c); Chronoamperometry measurements (I vs. t) recorded on S-6 at a constant applied potential of 0.31 V vs. Ag/AgCl (d). All the stability tests were conducted in deaerated H2SO4 aqueous solutions (0.5 M) at 25°C.

3. CONCLUSIONS In summary, we prepared N-doped carbon cages encapsulated PdCo alloy nanoparticles using Pd-doped MOFs as precursor. The catalyst exhibited excellent activity with low overpotential, small Tafel slope, as well as an outstanding electrochemical durability in HER evaluation even after 10000th cycling. This work shows that the alloy of noble metal can be directly obtained by annealing appropriate MOFs precursors. This study provides a navel way towards rational design



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and fabricate high-performance, super-stability HER electrocatalysts with minimal noble metal content.

ASSOCIATED CONTENT Supporting Information Experimental details and additional SEM, TEM, XPS, LSV, elemental mappings and EDX results; BET curves and Raman spectra

AUTHOR INFORMATION Corresponding Author E-mail: [email protected]

Notes The authors declare no competing financial interest.

ACKNOWLEDGMENTS

This study was supported by the National Natural Science Foundation (NSFC, 21271163, U1232211), CAS/SAFEA international partnership program for creative research teams

and CAS Hefei Science Center. The author Ren Li thanks for the financial support from China Scholarship council (CSC, 201500730008).

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Active and Durable Hydrogen Evolution Reaction Catalyst Derived

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