Surfactant-assisted Formation of Nanoporous Pt Particles as Co-catalyst Loaded on P25 and Enhanced Photocatalytic Performance†

doi:10.7503/cjcu20180823

Abstract

Abstract:

Highly dispersed PtNi alloy particles were loaded on P25 as co-catalyst by chemical reduction in the presence of surfactant polyvinylpyrrolidone(PVP) and octoxinol(Triton X-100). The PtNi alloy particles were then de-alloyed to remove Ni atoms of the alloy selectively to obtain Pt nanoparticles having surface nanoscale hollow pore structure. The obtained sample showed an excellent activity for degrading the methylene blue(MB) dye and photocatalytic hydrogen production as compared with the case without the use of surfactant. This beneficial effect was ascribed to the following key factors: (1) the nanoporous structure increased surface area and active sites for H₂ production; (2) longer active site residence time of photogenerated electrons and reactants which is attributed to a confinement effect within the nanoporous structures. At the same time, the experimental results show that OH· and · $O 2 -$ are the main active species of the photocatalytic degradation of MB.

Key words: Photocatalysis, Surfactant, Porous Pt, De-alloying, Cocatalyst

CLC Number:

O644

JI Lei,GUO Fanzuo,WANG Kehan,WANG Lei. Surfactant-assisted Formation of Nanoporous Pt Particles as Co-catalyst Loaded on P25 and Enhanced Photocatalytic Performance^†[J]. Chemical Journal of Chinese Universities, 2019, 40(7): 1501-1509.

Figures/Tables 14

Table 1 Mass fraction of Pt and Ni and dosage of P25 required

Sample	w(Pt)(%)	w(Ni)(%)	m(P25)/g
R-P25	0	0	0.2000
Pt/P25	3.0	0	0.1940
PtNi₂/P25	3.0	1.8	0.1904
PtNi₃/P25	3.0	2.7	0.1886
PtNi₄/P25	3.0	3.6	0.1868

Fig.1 SEM images of PtNi2/P25(A) and PtNi2(PT30)/P25(B) and TEM images of de-PtNi2/P25(C, D) and de-PtNi2(PT30)/P25(E, F)

Fig.2 SEM images(A, D) and Pt(B, E), Ni(C, F) EDS mapping of PtNi2/P25(A—C) and PtNi2(PT30)/P25(D—F)

Fig.3 EDS spectra of PtNi2(PT30)/P25 after dealloying in 2 mol/L H2SO4 solution for 0(A), 15(B), 30 min(C)

Table 2 Elemental composition of sample de-PtNi2(PT30)P25 with different dealloying time

Element	Mass fraction(%)			Atomic fraction(%)
Element	0 min	15 min	30 min	0 min	15 min	30 min
C	7.95	8.04	4.13	16.11	15.85	8.14
O	38.01	40.43	46.25	57.83	59.71	68.52
Ti	48.91	47.76	46.37	24.85	23.81	22.94
Ni	1.96	0.54	—	0.81	0.21	—
Pt	3.17	3.23	3.25	0.40	0.42	0.40

Fig.4 XRD patterns of the P25(a), Pt/P25(b), PtNi2/P25(c), de-PtNi2/P25(d) and de-PtNi2(PT30)/P25(e) samples

Table 3 Specific surface area, pore volume and average pore diameter of different samples

Sample	Specific surface area/(m²·g^-1)	Pore volume/(cm³·g^-1)	Aperture/nm
P25	49.0	0.20	16.2
Pt/P25	49.3	0.23	20.6
PtNi₂/P25	48.3	0.29	21.8
de-PtNi₂/P25	50.3	0.29	23.0
PtNi₂(PT₃₀)/P25	48.6	0.38	31.4
de-PtNi₂(PT₃₀)/P25	50.4	0.38	31.3

Fig.5 Photoluminescence spectra of the P25(a), R-P25(b), Pt/P25(c), PtNi2/P25(d), de-PtNi2/P25(e) and de-PtNi2(PT30)/P25(f) samples

Fig.6 Ultraviolet-visible diffuse reflectance spectra(A) and αhν0.5 versus photon energy(hν)(B) for samples

Fig.7 Photocatalytic degradation of MB in the presence of different catalysts under UV light irradiation(A) a. P25; b. R-P25; c. Pt/P25; d. de-PtNi/P25; e. de-PtNi2/P25; f. de-PtNi3/P25; g. de-PtNi4/P25. (C) a. P25; b. Pt/P25; c. PtNi2(PT30)/P25; d. de-PtNi2(PT0)/P25; e. de-PtNi2(PT15)/P25; f. de-PtNi2(PT20)/P25; g. de-PtNi2(PT30)/P25; h. de-PtNi2(PT35)/P35. (D) a. P25; b. Pt/P25; c. de-PtNi2(P0T)/P25; d. de-PtNi2(P0.17T)/P25; e. de-PtNi2(P0.033T)/P25; f. de-PtNi2(P0.050T)/P25; g. de-PtNi2(P0.067T)/P25.

Fig.8 Hydrogen evolution prformance of photocatalysts Pt/P25(a, a), de-PtNi2/P25(b, b) and de-PtNi2(PT30)/P25(c, c) under 300 W Xe lamp irradiation

Scheme 1 Schematic illustration of well-distributed nanoporous catalyst formation

Fig.9 Kapp values of P25 and de-PtNi2(PT30)/P25 in the presence of different scavengers

Scheme 1 Proposed mechanism for photogenerated charge carrier transfer in nanoporous Pt/P25 under UV irradiation

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