Photocatalytic

H2

production

on

Pt-PdS/CdS

with

quantum

efficiency exceeding 90% under visible light irradiation

Jinhui Yang, Hongjian Yan, Xiuli Wang, Fuyu Wen, Jingying Shi and Can Li* State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences and Dalian National Laboratory for Clean Energy, 457 Zhongshan Road, Dalian 116023, China

Photocatalytic production of H 2 as a potential means of converting solar energy to chemical energy now attracts much attention due to environmental crisis and energy shortage [1]. One key issue with regard to the energy conversion is the quantum efficiency (QE). Modifications to semiconductors by doping with foreign elements or by loading matching co-catalysts or by combinations with other semiconductors are able to reduce bulk, surface and interface recombination of photoinduced charges thereby increasing the QE [2]. We have demonstrated a successful example in terms of improving QE by coloading Pt and PdS as dual co-catalysts on CdS, which shows a QE of 93% for H 2 production in the presence of Na 2 S and Na 2 SO 3 as the sacrificial reagents (Table 1) [3]. The QE is comparable to that of that of the primary courses of natural photosynthesis. The mechanism of the extremely high QE and high stability over the three-component PtPdS/CdS photocatalyst is further investigated in order to shed a light on the photocatalysis mechanism.
Table 1 Photocatalytic H 2 evolution over CdS loaded with various co-catalysts.

Catalyst QE (%)

CdS 0.2

Pt/CdS 51

PdS/CdS 64

Pt-PdS/CdS 93 and high

In situ photoelectrochemical measurements, photoluminescence resolution transmission electron microscopy (HRTEM)

characterizations are

employed to clarify the catalytic role of co-catalysts (Pt and PdS) in achieving the exceptionally high QE (Fig. 1). These characterizations indicate that PdS and Pt respectively play the role of oxidation and reduction active sites, the existence of PdS can utilize the shallow states of CdS near surface region of CdS and the atomic junctions are formed between the co-catalyst and CdS. These are crucially responsible for the exceptionally high QE and stability.

Fig. 1 (A) Current density-potential (j - E) curves in the dark (solid line) and under illumination (dash dot line). (B) Photoluminescence spectra of CdS, Pt/CdS, PdS/CdS and Pt-PdS/CdS powders. (C) Highresolution Transmission Electron Microscopy (HRTEM) images of PdS/CdS. Inset shows magnified Fourier-filtered inversion of the lattice spacing of CdS and PdS.

The combination of Pt with other metal sulfides and PdS with other noble metals as dual co-catalysts show enhancement in activity compared to any single co-catalysts loaded (Fig. 2A). The effect of Pt and PdS co-loaded on other semiconductors shows that the photocatalytic activities are all in the order of Pt/MS < PdS/MS < Pt-PdS/MS, with the trend similar to those for CdS (Fig. 2B). A B

Fig. 2 Photocatalytic H 2 evolution activities over (A) combinations of metals and metal sulfides as dual co-catalysts loaded on CdS (B) sulfide photocatalysts loaded with Pt, PdS and Pt-PdS.

This work highlights the photocatalytic activity dependence on the dual cocatalysts respectively acting as the reduction and oxidation active sites. The utilization of shallow state by co-catalysts shown by the quench of fluorescence and the formation of atomic junctions between the semiconductor CdS and co-catalysts are also crucial. The crucial role of dual co-catalysts has been demonstrated to be true for other sulfide based photocatalysts for photocatalytic H 2 production.
References [1] X. Chen, S. Shen, L. Guo, S.S. Mao, Chem. Rev. 110 (2010) 6503. [2] X. Zong, H. J. Yan, G.P. Wu, G.J. Ma, F.Y. Wen, L. Wang, C. Li, J. Am. Chem. Soc. 130 (2008) 7176. [3] H. Yan, J. Yang, G. Ma, G. Wu, X. Zong, Z. Lei, J. Shi, C. Li, J. Catal. 266 (2009) 165.