Supporting Information. Molybdenum Polysulfide Anchored on Porous Zr Metal Organic Framework to Enhance the Performance of Hydrogen Evolution Reaction

Transcription

1 Supporting Information Molybdenum Polysulfide Anchored on Porous Zr Metal Organic Framework to Enhance the Performance of Hydrogen Evolution Reaction Xiaoping Dai, *,, Mengzhao Liu,, Zhanzhao Li, Axiang Jin, Yangde Ma, Xingliang Huang, Hui Sun, Hai Wang, Xin Zhang *, a State Key Laboratory of Heavy Oil Processing, China University of Petroleum, Beijing , China b National Institute of Metrology, Beijing , China E mail: daixp@cup.edu.cn; zhangxin@cup.edu.cn Synthesis of Control Samples S2 Supporting figures and table S3-S16 References S17-S19 S1

2 Synthesis of Control Samples Synthesis of bulk MoS2 The bulk MoS2 was prepared with a hydrothermal method. Typically, 22.4 mg of (NH4)2MoS4 was added into 10 ml of DMF solution and sonicated for approximately 20 min at room temperature until a homogeneous solution was achieved. After that, 0.1 ml of N2H4 H 2O was added to the above solution and was further sonicated for 10 min before transferred to a 25 ml Teflon lined autoclave. It was heated in an oven at 220 C for 24 h and cooled down to room temperature naturally. Product was collected by centrifugation at 9000 rpm for 15 min, washed with DI water and ethanol at least three times respectively to remove DMF. Finally, product was re dispersed in DI water with a concentration of 1 mg/ml, and dried with freeze drying equipment, which was donated as bulk MoS2. Preparation of UiO 66 In a typical synthesis, ZrCl4 (149 mg, 0.64 mmol) and Terephthalic acid (TA, 106 mg, 0.64 mmol) were thoroughly dissolved in DMF (18 ml), and were further sonicated for 10 min. It was transferred into a 40 ml Teflon lined stainless steel autoclave, which was then sealed and heated at 100 o C for 24 h. After cooling, the resultant precipitate was collected by centrifugation, and washed with absolute ethanol for several times, followed by drying under vacuum at 80 o C for 10 h. Preparation of molybdenum polysulfide anchored UiO 66 The synthetic procedure of molybdenum polysulfide anchored UiO 66 was similar as the original UiO 66, except for the addition of (NH 4) 2MoS 4 before solvothermal treatment. The obtained sample was denoted as UiO 66 Mo 5 with mole ratio of Mo/Zr=0.5. S2

3 Intensity(a.u.) Theta (Degree) Figure S1 Comparison of XRD patterns of UiO 66 NH2 Mo 5. Bottom: As synthesized MOFs (from DMF). Top: Ethanol exchanged MOFs. S3

4 Transmittance (%) UiO UiO-66-Mo Wavenumber (cm -1 ) Figure S2 FTIR spectra of UiO 66 and UiO 66 Mo 5. S4

5 A 1 μm B a 8 Layers 5nm D=0.62 nm Figure S3 (A) SEM and (B) TEM images of bulk MoS2. S5

6 A Frequency (%) Average=135±7 nm Size distribution (nm) 1 μm B Frequency (%) Average=33±10 nm Size distribution (nm) 1 μm Figure S4 SEM images and EDS of (A) UiO 66 NH2 and (B) UiO 66 NH2 Mo 5. S6

7 Table S1 Elemental composition in the as prepared samples from elemental and ICP analyses Samples Mass percentage (wt. %) Elemental analyses ICP analyses C N H S Zr Mo Mo/Zr (atom ratio) S/Mo (atom ratio) UiO 66 NH UiO 66 NH2 Mo UiO 66 NH2 Mo UiO 66 NH2 Mo UiO 66 NH2 Mo S7

8 A C-C & C-H (sp 2 ) C1s B Zr3d C-N C=O Intensity (a.u.) b Intensity (a.u.) b a a Binding Energy (ev) Binding Energy (ev) C O1s D N1s Mo2p 3/2 Intensity (a.u.) b Intensity (a.u.) c a a Binding Energy (ev) Binding Energy (ev) Figure S5 XPS spectra for (A) C1s, (B) Zr3d, (C) O1s, (D) N1s Mo2p for (a) UiO 66 NH2, (b) (NH4)2MoS4 and (c) UiO 66 NH2 Mo 5. S8

9 Currrent/ ma cm Potential /V vs.rhe Figure S6 Polarization curve of bulk MoS2. S9

10 Table S2 Comparison of HER performance in acid media for UiO 66 NH 2 Mo 5 with other HER electrocatalysts. Catalyst Electrolyte Catalyst loading (mg/cm 2 ) Overpotential at 10 ma/cm 2 (mv) Tafel (mv dec 1.) Ref. Co 9S 8@MoS 2/CNFs 0.5 M H 2SO Co 0.6Mo 1.4N M HClO / 2 Amorphous MoS x 0.5 M H 2SO 4 / MoS 3/CNT 1.0 M H 2SO Defect rich MoS M H 2SO MoS 2/3D-NPC 0.5 M H 2SO MoS 2/PANI 0.5 M H 2SO Cu MoS 2/rGO 0.5 M H 2SO MoS 2 MoN/N C 0.5 M H 2SO Cu 2MoS M H 2SO Ni MoS M H 2SO Se MoS M H 2SO NiMoN x/c 0.1 M HClO > Porous MoC x 0.5 M H 2SO Mo 2C@NCNTs 0.5 M H 2SO Co NRCNTs 0.5 M H 2SO Co@NC/NG 0.5 M H 2SO N Co@G 0.5 M H 2SO Co@N C 1 M HClO Ni-S/NU M HCl POM based MOF 0.5 M H 2SO (GO 8 wt.%) Cu MOF 0.5 M H 2SO UiO 66 NH 2 Mo M H 2SO This work S10

11 Current density(ma/cm 2 ) 0 UiO UiO-66-Mo-5-40 UiO-66-NH2-Mo-5 Pt/C Potential (V vs. RHE) Figure S7 Polarization curves of UiO 66, UiO 66 NH2 Mo 5 and UiO 66 Mo 5 in 0.5 M H2SO4. S11

12 bulk MoS 2 -Z'' ( ) Z' ( ) Figure S8 EIS nyquist plots of bulk MoS2. S12

13 5 nm Figure S9 HRTEM image of the UiO 66 NH2 Mo 5 after the stability test. S13

14 0.30 Potential (V vs. RHE) UiO-66-NH 2 -Mo-1 UiO-66-NH 2 -Mo-6 UiO-66-NH 2 -Mo-5 UiO-66-NH 2 -Mo Exchange current density (A/cm 2 ) Pt/C Figure S10 Exchange current densities of UiO 66 NH2 Mo x by applying extrapolation method of Tafel plots. S14

15 a Scan rate b Scan rate Current density (ma/cm -2 ) Current density (ma/cm -2 ) Potential (V vs. RHE) Potential (V vs. RHE) 0.9 c Scan rate 0.6 Current density (ma/cm -2 ) Potential (V vs. RHE) Figure S11 Cyclic voltammograms ( V) recorded in 0.5 M H2SO4 for (a) UiO 66 NH2 Mo 1, (b) UiO 66 NH2 Mo 3 and (c) UiO 66 NH2 Mo 6. S15

16 Current (A) GCE Potential (V vs. RHE) Figure S12 Cyclic voltammograms of bare GCE recorded at ph =7 phosphate buffer with a scan rate of 50 mv s 1. S16

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