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3.3 XPS results
To discuss the oxidation state of Co species, the XPS spectra of Co 2p3/2 and Co 2p1/2 levels for Ag-containing catalysts are shown in Fig. 3a. It is known that the negative shifts of Co 2p3/2 peaks were due to the existence of higher oxidation state of Co4+ [9, 18]. The binding energy of Co 2p3/2 is only 779.3 eV even after the presence of some Co4+ ions in La1-xKxCoO3 perovskites. The binding energy of Co 2p3/2 is about 780.0 eV in present work, which is close to the binding energy of Co in LaCoO3 (779.7) and Co3+ in Co2O3 (779.6 eV)[13][ 20140619-44], Thus, Co species should exist as the low valence (Co2+ and Co3+) instead of Co4+. This result is in accordance to XRD and TPR results.
Fig. 3b shows the XPS spectra of Ag species. For all samples, there are two main binding energy peaks corresponding to Ag 3d5/2 and Ag 3d3/2 levels at 368.2 eV and 374.2 eV with spin orbit separation of 6.0 eV. It has been reported that [14][ 20141011-15, [21] M. Kumar, G.B.  Reddy,  Phys  Status  Solidi  B  246  (2009)  2232¨C2237.], Ag 3d5/2 peak at 368.2 eV indicates that Ag species exist as metallic Ag (Ag0) and Ag 3d5/2 peak , at 367.8 eV in the range 367.3¨C368.6 eV suggest Ag species exist as Ag+ and Ag2+, respectively. Therefore, Ag species in the surface of Ag/LaCoO3 is speculated to be mainly metallic state. The high symmetry of Ag 3d5/2 peak suggests the relatively homogeneous environment of Ag0.
XPS spectra of O1s are demonstrated in Fig. 3c. For La1-XM1XCo1-YM2YO3 perovskites, it was suggested that the binding energy attributed to adsorbed oxygen in oxygen vacancy is 530.8 eV [9], that of chemisorbed oxygen and lattice oxygen are 532.7 eV [17], and 529.8 eV, respectively. [Co0.93La0.07 samples.] Ag/LaCoO3 displayed two peaks. The peak with a lower binding energy (528.6 eV) was assigned to lattice oxygen (Olat). The peak with higher binding energy (531.3-531.6 eV) was attributed to absorbed oxygen (Oads). The content of Oads species is as high as 67.7% on the surface of Ag/LaCoO3-400, which is much higher than that on the surface of Ag/LaCoO3-800 ( 56.6% ) and the data reported in previous works [ ]. This should be caused by the presence of more Ag0.
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3.3 XPS²â¶¨½á¹û

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ͼ3bÁгöÒøÎïÖÖµÄXPS¹âÆ×¡£¶ÔÓÚÈ«²¿ÑùÆ·,¶ÔÓ¦ÓÚÒø3d5/2ºÍÒø3d3/2ÔÚ368.2 eVºÍ374.2 eV´¦ÓÐÁ½¸ö×ÔÐý¹ìµÀ·ÖÀëΪ6.0 eVµÄ¼üÄÜÖ÷·å¡£It hÒÑÓб¨µÀ[14][20141011-15,[21] M.Kumar,G.B.Reddy, Phys Status Solidi B 246 (2009)2232-2237]˵ÔÚ368.2 eV´¦µÄÒø3d5/2·å±íÃ÷ÒÔ½ðÊôÒø(Ag0)ÐÎ̬´æÔÚµÄÒøÎïÖÖºÍÔÚ367.8 eV´¦µÄÒø3d5/2£¨²â³ÌΪ367.3-368.6 eV£©·å·Ö±ð±íʾÒÔAg+ºÍAg2+ÐÎ̬´æÔÚµÄÒøÎïÖÖ¡£ËùÒÔ,¾ÝÍÆ²âÔÚÒø/LaCoO3±íÃæµÄÒøÎïÖÖΪÖ÷Òª½ðÊô״̬¡£Òø3d5/2·åµÄ¸ß¶Ô³ÆÐÔÏÔʾÁËAg0µÄÏà¶Ô¾ùÔÈ»·¾³¡£
O1sµÄXPS¹âÆ×ÏÔʾÓÚͼ3c¡£¶ÔÓÚLa1-XM1XCo1-YM2YO3¸ÆîÑ¿ó,é§ÈÏΪ¹éÒòÓÚÑõȱλÖÐÎü¸½ÑõµÄ¼üÄÜΪ530.8 eV [9],»¯Ñ§Îü¸½µÄÑõºÍ¾§¸ñÑõµÄ¼üÄÜ·Ö±ðΪ532.7 eV [17]ºÍ529.8 eV¡£[ Co0.93La0.07ÑùÆ·]Òø/LaCoO3ÏÔʾ³öÁ½¸ö·å¡£¾ßÓнϵͼüÄÜ(528.6 eV)µÄ·å¹éÊôÓÚ¾§¸ñÑõ(Olat)¡£¾ßÓнϸ߼üÄÜ(531.3-531.6 eV)¿É¹éÊôÓÚÎü¸½Ñõ(Oads)¡£Òø/ LaCoO3 - 400±íÃæÉÏOadsÎïÖֵĺ¬Á¿¸ß´ï67.7%£¬ÕâÒª±ÈÒø/LaCoO3 - 800±íÃæÉϵĺ¬Á¿(56.6%)ºÍÒÔÍùµÄÑо¿ÖеÄÊÔÑéÊý¾Ý±¨¸æ¸ßºÜ¶à¡£ ÕâÊÇÓɸü¶àAg0µÄ´æÔÚËùÒýÆð¡£
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