Interfacial synergism of Pd-decorated BiOCl ultrathin nanosheets for selective oxidation of aromatic alcohols

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1 Electronic Supplementry Mteril (ESI) for Journl of Mterils Chemistry A. This journl is The Royl Society of Chemistry 2018 Interfcil synergism of Pd-decorted BiOCl ultrthin nnosheets for selective oxidtion of romtic lcohols Benxi Li* [], Lingzhi Sho [], Renshn Wng [], Xioping Dong [], Fugng Zho [], Peng Go [b], Zhengqun Li [c] [] Deprtment of Chemistry, College of Science, Zhejing Sci-Tech University, Hngzhou , P. R. Chin [b] College of Mteril, Chemistry nd Chemicl Engineering, Hngzhou Norml University, Hngzhou, Zhejing , P. R. Chin [c] Key Lbortory of the Ministry of Eduction for Advnced Ctlysis Mterils, Zhejing Norml University, Jinhu, Zhejing , P. R. Chin *Corresponding Author. Benxi Li: Figure S1. Schemtic digrm of the experiment set-up for photoctlytic rections. 1

2 Figure S2. () XRD pttern, (b) SEM imge, nd (c) TEM imge of BiOCl ultrthin nnosheets. Figure S3. XRD ptterns of () Au-BiOCl nd (b) Pd-BiOCl smples. 2

3 Figure S4. Optimized structures of () BiOCl(001), (b) Au-BiOCl(001), nd (c) Pd- BiOCl (001) surfce models with V O site. Figure S5. CBM nd VBM of (-b) BiOCl(001), (c-d) Au-BiOCl(001), nd (e-f) Pd- BiOCl (001). 3

4 Figure S6. CBM nd VBM of the different mteril systems with the dsorbed O 2. (b) bre, (c-d) Au decorted, (e-f) Pd decorted BiOCl (001) with V O site, respectively. 4

5 Figure S7. CBM nd VBM of the different mteril systems with the dsorbed benzyl lcohol. (-b) bre, (c-d) Au decorted, (e-f) Pd decorted BiOCl (001) with V O site, respectively. Figure S8. Schemtic illustrtions for photoctlytic rections crried out in ir nd pure O 2 tmosphere, respectively. 5

6 Tble S1. Theoreticl nd ICP-OES mesured metl loding mounts of the photoctlysts. Smple Theoreticl Au(or Pd) Actul Au (or Pd) contents (wt.%) contents (wt.%) b Au-BiOCl Pd-BiOCl The theoreticl metl loding mss percent clculted from the experimentl dosge of HAuCl 4 or (NH 4 ) 2 PdCl 4 for photo-deposition. b The ctul mss percent of metl in ech photoctlyst from the ICP-OES mesured results. Tble S2. The Hirshfeld chrge of ech tom in the different mteril systems nd the dsorption energies for O 2 (E ds+o2 ) nd C 7 H 8 O (E ds+c7h8o ) on different surfces, respectively. System e Bi e Cl e O e M E ds+o2 (ev) BiOCl Au-BiOCl Pd-BiOCl 0.09*2 0.35*2 0.48*4 0.56* *4 0.42*4 0.56* *4 0.35*2 0.48*2 0.57* * *3-0.22* * *6-0.22* * * * *4-0.35* *4-0.34* * * *1-0.01*3-0.03*4-0.04*4-0.02*2-0.04*4-0.07*3-0.09*3 E ds+c7h8o (ev)

7 Tble S3. Lifetimes ( 1, 2 nd m ) nd reltive intensities (A i ) obtined by fitting the time-resolved PL decy spectr of BiOCl, Au-BiOCl nd Pd-BiOCl to bi-exponentil decy function. Smple BiOCl Au-BiOCl Pd-BiOCl verge lifetime, m τ 1 /ns(int 1 ) τ 2 /ns(int 2 ) 0.295(0.868) 0.298(0.878) 0.800(0.828) A1 1 A2 2 A A (0.132) 3.200(0.122) 3.597(0.172) τ m /ns Tble S4. Photoctlytic oxidtion of benzyl lcohol to benzldehyde over the different photoctlysts under UV-vis irrdition for 8 h. Photoctlyst Atmosphere Conversion (%) Yield(%) selectivity (%) BiOCl Air >99 L-BiOCl Air >99 Au-BiOCl Air >99 Air >99 Pd-BiOCl O >99 N >99 Pd/BiOCl* Air >99 In typicl rection, 1 mg of ctlyst ws dded to 2 ml of cetonitrile in qurtz tube, 50 μmol of benzyl lcohol were injected into the qurtz tube. Keep the qurtz tube seled nd strt illuminting. *The Pd/BiOCl smple ws prepred by simply soking BiOCl nnosheets into Pd nnoprticles solution which ws obtined by the reduction of (NH 4 ) 2 PdCl 4 using NBH 4. 7

8 Tble S5. Photoctlytic selective oxidtion of vrious romtic lcohols to corresponding ldehydes over Pd-BiOCl under UV-vis irrdition for 8 h Aromtic lcohol Conversion (%) Yield (%) Selectivity (%) Benzyl lcohol >99 4-Methylbenzyl lcohol >99 4-Methoxybenzyl lcohol >99 Cinnmyl lcohol >99 2-Phenylethnol >99 In typicl rection, 1mg of ctlyst ws dded to 2 ml of cetonitrile in qurtz tube, 50 μmol of romtic lcohol were injected into the qurtz tube. Keep the qurtz tube seled nd strt illuminting. Tble S6. Photoctlytic oxidtion of benzyl lcohol to benzldehyde over Pd-BiOCl by dding different scvengers under UV-Vis irrdition for 8 h. Scvenger Conversion (%) Yield (%) Selectivity (%) No scvenger >99 IPA >99 BQ >99 EDTA-2N >99 In typicl rection, 1mg of ctlyst ws dded to 2 ml of cetonitrile in qurtz tube, 50 μmol of benzyl lcohol nd 0.05mol/L scvengers were injected into the qurtz tube. Keep the qurtz tube seled nd strt illuminting. 8