Metal-doped Mo2C (metal = Fe, Co, Ni, Cu) as catalysts on TiO2 for photocatalytic hydrogen evolution in neutral solution

doi:10.1016/S1872-2067(20)63589-6

Abstract

Abstract:

The neutral hydrogen evolution reaction (HER) is vital in the chemical industry, and its efficiency depends on the interior character of the catalyst. Herein, work function (W_F) engineering is introduced via 3d metal (Fe, Co, Ni, and Cu) doping for modulating the Fermi energy level of Mo₂C. The defective energy level facilitates the free water molecule adsorption and, subsequently, promotes the neutral HER efficiency. Specifically, at a current density of 10 mA/cm², Cu-Mo₂C exhibits the best HER performance with an overpotential of 78 mV, followed by Ni-Mo₂C, Co-Mo₂C, Fe-Mo₂C, and bare Mo₂C with 90, 95, 100, and 173 mV, respectively, and the corresponding Tafel slope values are 40, 43, 42, 56, and 102 mV/dec. The modified W_F can also lead to an enhanced photocatalytic efficiency owing to the lowered Schottky barrier and excellent carrier transition across the electrocatalyst-solution interface. When coupling the metal-doped Mo₂C samples with TiO₂, enhanced photocatalytic neutral HER rates are obtained in comparison to the case with bare TiO₂. Typically, the HER rates are 521, 404, 275, 224, 147, and 112 μmol/h for Cu, Ni, Co, Fe, bare Mo₂C, and bare TiO₂, respectively. Time-resolved photoluminescence spectroscopy (TRPS) and ultrafast transient absorption (TA) measurements are carried out to confirm the recombination and migration of the photogenerated carriers. The fitted τ values from the TRPS curves are 22.6, 20.5, 10.1, 4.7, 4.0, 2.5, and 1.9 ns for TiO₂, TiO₂-Mo₂C, TiO₂-Fe-Mo₂C, TiO₂-Fe-Mo₂C, TiO₂-Fe-Mo₂C, TiO₂-Fe-Mo₂C, and TiO₂-Pt, respectively. Additionally, the fitted τ values from the TA results are 31, 73, and 105 ps for the TiO₂-Mo₂C, TiO₂-Cu-Mo₂C, and TiO₂-Pt samples, respectively. This work provides in-depth insights into the W_F modulation of an electrocatalyst for improving the HER performance.

Key words: 3d metal, Doping, Mo₂C, TiO₂, Photocatalysis, Water splitting, Hydrogen evolution

Jing Liu, Gary Hodes, Junqing Yan, . Metal-doped Mo₂C (metal = Fe, Co, Ni, Cu) as catalysts on TiO₂ for photocatalytic hydrogen evolution in neutral solution[J]. Chinese Journal of Catalysis, 2021, 42(1): 205-216.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(20)63589-6

https://www.cjcatal.com/EN/Y2021/V42/I1/205

Figures/Tables 9

Fig. 1. Schematic diagram of the electron tunnel transition across the electrode-solution interface, (a) the bare and (b) the doped catalyst systems. Evac, vacuum level; Ef, Fermi level; φ, work function; WO and WR are the reduction and oxidation energy levels of the O/R redox couples; E0f(O/R), the defined quasi-Efermi of the redox couple; the electronic energy level of the electrode is scaled by Evac, and the redox couple is the standard hydrogen electrode (SHE). The doping energy level is also shown in b.

Fig. 2. Preparation process of bare and MOx-coated Mo2C. (a) Schematic illustration of the synthesis of metal-doped Mo2C: i) the MOx precursors (metal chlorates) were dropwise added into the MoO3 solution; ii) after stirring the above mixture, the metal oxides were formed on the surface of MoO3; iii) the M-MoO3 samples were mixed uniformly with urea and subsequently calcined in N2 at 600 °C. (i) The ellipsoid indicates MoO3, (ii) and the small black dots indicate the metal oxides. (b) The XRD patterns of M-MoO3; (c) XRD patterns of M-Mo2C.

Fig. 3. X-ray photoelectron spectroscopy (XPS) spectra of M-Mo2C. (a) Mo 3d of the bare and metal-doped Mo2C, (b) Ni 2p, (c) Cu 2p, (d) Fe 2p, and (e) Co 2p XPS spectra.

Fig. 4. HER performance of Mo2C-based samples. (a) Polarization curves recorded on glassy carbon electrodes. For all the samples, the catalyst loading was 0.2 mg/cm2, and the scan rate was 5 mV/s. (b) The corresponding Tafel plots, derived from the polarization curves in (a). (c) The overpotentials of the samples for the current densities of 10, 50, and 500 mA/cm2, also derived from the polarization results. (d) Electrochemical impedance spectroscopy (EIS), performed under the given applied potential of -0.1 V (vs. RHE). (e) The plots of ?j at 1.3 V vs. RHE against the scan rate; data obtained from the cyclic voltammetry (CV) curves in the region of 1.2-1.4 V vs. RHE are given in Figure S6. (f) Durability test of the undoped and doped Mo2C catalysts at the applied potential of -0.1 V (vs. RHE). All samples were tested for 600 s.

Table 1 Summary of the HER performance of the undoped and metal-doped Mo2C in 0.5 M Na2SO4.

Sample	R_s (Ω/cm²)	R_ct (Ω/cm²)	η₁₀(mV)	η₅₀(mV)	η₁₀₀(mV)	Tafel (mV/dec)	SSA ^a(m²/g)	C_dl^b(F/cm²)
Mo₂C	5.92	119	173	283	360	102	12.3	0.047
Fe-Mo₂C	5.83	89.6	100	161	200	56	11.7	0.06
Co-Mo₂C	5.83	46.5	95	145	178	42	13.4	0.1
Ni-Mo₂C	5.69	33.8	90	137	172	43	10.8	0.16
Cu-Mo₂C	5.88	23.2	78	127	160	40	11.9	0.24

Fig. 5. Physico-chemical properties of the bare TiO2 and TiO2-M-Mo2C samples. (a) XRD patterns; (b) UV-Vis-NIR diffuse reflection (K-M absorption) spectra; (c) Room-temperature PL spectra; (d) Ti 2p XPS peaks.

Fig. 6. Photocatalytic HER performance of TiO2-M-Mo2C samples. (a) HER activity, 2% TiO2-Pt was used as the reference sample. (b) The hydrogen evolution rate with mean errors. (c) The stability test of the TiO2-Cu-Mo2C sample. The reference Pt sample was prepared by photodeposition. For the cycle measurements, the catalyst was treated via centrifugation, dried, and reused six times, and the reaction time was 12 h.

Fig. 7. (a) Time-resolved PL spectra of all samples; the excitation and emission wavelengths are 320 and 390 nm, respectively. The ultrafast transient absorption kinetics of (b) TiO2-Mo2C, (c) TiO2-Cu-Mo2C, and (d) the TiO2-Pt reference. The pump wavelength is 320 nm, and the probed wavelength is 525 nm.

Fig. 8. Mechanism of metal doping for promoting carrier transfer at the interfaces. (a) UPS of the different Mo2C samples. (b) The corresponding energy level schematic diagrams of the bare and metal-doped Mo2C. (c) FTIR intensity of the adsorbed water molecules on the bare and metal-doped Mo2C. The in-situ FTIR was carried out by a water-saturated N2 flow; (d) the near-linear relationship between the WF and the HER overpotential of the metal-doped Mo2C samples.

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Metal-doped Mo₂C (metal = Fe, Co, Ni, Cu) as catalysts on TiO₂ for photocatalytic hydrogen evolution in neutral solution

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