Tris(hydroxymethyl)aminomethane Modified Layered Double. Hydroxides Largely Facilitate Polyoxometalate Intercalation

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1 Electronic Sulementary Material (ESI) for Dalton Tranaction. Thi journal i The Royal Society of Chemitry 214 Suorting Information Tri(hyroxymethyl)aminomethane Moifie Layere Double Hyroxie Largely Facilitate Polyoxometalate Intercalation Yang Chen, Dongeng Yan, an Yu-Fei Song* State Key Laboratory of Chemical Reource Engineering, Beijing Univerity of Chemical Technology, Beijing 129, P. R. China.

2 Figure S1. Power XRD attern of the LDH-CO 3 an LDH-PW 11. Figure S2. Soli-tate 13 C CP/MAS NMR ectra of Tri-LDH-CO 3. Figure S3. Energy ierive X-ray (EDX) of Tri-LDH-PW 12.

3 Table S1. Elemental Comoition of LDH Samle (mmol/g). Samle Mg Al W N Tri-LDH-CO Tri-LDH-PW Calculation etail an analyi of Tri-LDH-CO 3 an Tri-LDH-PW 12. Builing of the tructural moel of LDH-CO 3, LDH-PW 12, Tri-LDH-CO 3 an Tri-LDH- PW 12 ytem an comutational metho: An ieal LDH layer (Figure S4b) with R3-m ace grou containing 17 Mg atom an 7 Al atom (Mg/Al ratio of 2.48, cloe to the exerimental value) wa built. The lattice arameter of the 2-imenional layer are a = b = 3.5 Å, which i in accorance with other literature. [S1] Each octaheral layer ha 24 metal atom an 48 OH grou, an a uercell wa contructe with lattice arameter a =1.57 Å, b = 18.3 Å, c = 7.9 Å an 1.3 Å for LDH-CO 3 an LDH-PW 12, reectively; α = β =γ = 9. The uercell wa treate a P1 ymmetry, an a three-imenional erioic bounary conition wa alie. For LDH-CO 3, four CO 3 anion were introuce into the imulate LDH uercell; for LDH-PW 12, one PW 12 O 4 anion (Figure S4c), two CO 3 anion an one NO 3 anion were introuce into the imulate LDH uercell, A a reult, the formula of the imulate tructure of LDH-CO 3 an LDH-PW 12 can be exree a: Mg 17 Al 7 (OH) 48 (CO 3 ) 3 (NO 3 ), Mg 17 Al 7 (OH) 48 (PW 12 O 4 )(CO 3 ) 2. For Tri moifie LDH layer, one or two tri(hyroxymethyl)aminomethane (Tri) molecule (Figure S4a) wa irectly anchore onto the LDH layer to form C-O-Mg or C-O-Al covalent bon, an the Tri- LDH-CO 3 an Tri-LDH-PW 12 can be exree a Mg 17 Al 7 (OH) 45 (C 4 H 8 NO 3 ) 1 (CO 3 ) 4, Mg 17 Al 7 (OH) 42 (C 4 H 8 NO 3 ) 2 (OH) 2-3y (CO 3 ) 4, an Mg 17 Al 7 (OH) 45 (C 4 H 8 NO 3 ) 1 (PW 12 O 4 )(CO 3 ) 2, Mg 17 Al 7 (OH) 42 (C 4 H 8 NO 3 ) 2 (PW 12 O 4 )(CO 3 ) 2. All calculation were erforme with the erioic enity functional theory (DFT) metho uing Dmol3 [S2a,b] moule in Material Stuio oftware ackage. [S2c] The initial configuration wa firt fully otimize with fixe oition for the atom in the layer by claical molecular mechanic metho emloye cff91 force fiel, [S2-f] then further otimization wa imlemente by Perew-Wang (PW91) [S2g] generalize graient aroximation (GGA) metho with the ouble numerical bai et lu olarization function (DNP). The core electron for metal were treate by effective core otential (ECP). SCF converge criterion wa within hartree/atom an converge criterion of tructure otimization wa

4 hartree/bohr. The Brillouin zone i amle by k-oint, an tet calculation reveal that the increae of k-oint oe not affect the reult. Figure S4. a). the tructural moel of tri(hyroxymethyl)aminomethane (Tri); b) the tetragonal uerlattice moel for LDH layer (color coe: white: H; re: O; ink: Al; green: Mg), c). tructural moel of PW 12, (PW 12 O 4 ) 3. Table S2. Calculate lattice energy of LDH-CO 3, Tri-LDH-CO 3, LDH-PW 12, an Tri-LDH-PW 12. Samle LDH-CO 3 Tri 1 -LDH-CO 3 Tri 2 -LDH-CO 3 Energy (hartree) Samle LDH-PW 12 Tri 1 -LDH-PW 12 Tri 2 -LDH-PW 12 Energy (hartree) Tri 1 -LDH-CO 3 : Mg 17 Al 7 (OH) 45 (C 4 H 8 NO 3 ) 1 (CO 3 ) 4 ; Tri 2 -LDH-CO 3 : Mg 17 Al 7 (OH) 42 (C 4 H 8 NO 3 ) 2 (OH) 2-3y (CO 3 ) 4 ; Tri 1 -LDH-PW 12 : Mg 17 Al 7 (OH) 45 (C 4 H 8 NO 3 ) 1 (PW 12 O 4 )(CO 3 ) 2 ; Tri 2 -LDH-PW 12 : Mg 17 Al 7 (OH) 42 (C 4 H 8 NO 3 ) 2 - (PW 12 O 4 )(CO 3 ) 2. To etect the influence of the ifferent moel on the calculation reult, a Mg-Al- LDH uercell (Figure S5) wa further electe to accommoate the ure PW 12 anion in the abence of intercalate CO 2-3. In thi cae, a new layer moel (enote a Moel 2) containing 9 Mg atom an 3 Al atom wa built a hown in Figure S5 (equivalent to a uer cell), an one PW 12 anion with -3 charge can be irectly aemble into the LDH without other anion. The formula of three moel can be exree a: Mg 9 Al 3 (OH) 24 (PW 12 O 4 ) (a Pure LDH-PW 12 ), Mg 9 Al 3 (OH) 21 (C 4 H 8 NO 3 )(PW 12 O 4 ) (a Pure Tri 1 -LDH-PW 12 ), an Mg 9 Al 3 (OH) 18 (C 4 H 8 NO 3 ) 2 - (PW 12 O 4 ) (a Tri 2 -LDH-PW 12 ). All calculation were erforme with the ame conition in Material Stuio oftware ackage.

5 Figure S5. A). The LDH layer (enote a moel 2; uer cell), an B). Structural moel of PW 12, (PW 12 O 4 ) 3. Table S3. Calculate lattice energy of LDH-PW 12 an Tri-LDH-PW 12 (Moel 2) Samle Pure LDH-PW 12 Pure Tri 1 -LDH-PW 12 Pure Tri 2 -LDH-PW 12 Energy (hartree) Pure LDH-PW 12 : Mg 9 Al 3 (OH) 24 (PW 12 O 4 ); Pure Tri 1 -LDH-PW 12 : Mg 9 Al 3 (OH) 21 (C 4 H 8 NO 3 ) 1 (PW 12 O 4 ); Pure Tri 2 -LDH-PW 12 : Mg 9 Al 3 (OH) 18 (C 4 H 8 NO 3 ) 2 (PW 12 O 4 ). Figure S6. Frontier orbital (HOMO an LUMO) of the DFT-otimize ure LDH-PW 12 (A), ure Tri 1 -LDH- PW 12 (B), an ure Tri 2 -LDH-PW 12 (C) tructure viewe from [1] irection; the two color onate +/- wavefunction.

6 DOS er electron/ev Figure S7. electronic enitie of tate (TDOS) in the LDH-PW 12 ytem. (the Fermi energy level wa et a zero). DOS er electron/ev a DOS er electron/ev b Figure S8. Partial electronic enitie of tate (PDOS) in the LDH-PW 12 ytem. (the Fermi energy level wa et a zero). Figure S9. Frontier orbital (HOMO (a) an LUMO (b)) of the DFT-otimize LDH-PW 12 tructure viewe from [1] irection; the two color onate +/- wavefunction.

7 DOS er electron/ev Figure S1. electronic enitie of tate (TDOS) in the Tri-LDH-PW 12 ytem. (the Fermi energy level wa et a zero). DOS er electron/ev a DOS er electron/ev b Figure S11. Partial electronic enitie of tate (PDOS) in the Tri-LDH-PW 12 ytem. (the Fermi energy level wa et a zero). Figure S12. Frontier orbital (HOMO (a) an LUMO (b)) of the DFT-otimize Tri-LDH-PW 12 tructure viewe from [1] irection; the two color onate +/- wavefunction.

8 Figure S13. The XRD attern of the Tri-LDH-PW 12 an the recycle Tri-LDH-PW 12 for ten time. Figure S14. FT-IR ectra of the Tri-LDH-PW 12 an the recycle Tri-LDH-PW 12 for ten time. Figure S15. 1 H NMR (CDCl 3 ) ectra of DBT, DBTO 2 (tanar), the oxiative rouct DBTO 2 (freh catalyt) an DBTO 2 (the recycle catalyt for ten time).

9 Reference [S1] D. P. Yan, J. Lu, L. Chen, S. H. Qin, J. Ma, M. Wei, D. G. Evan, X. Duan, Chem. Commun., 21, 46, [S2] a) B. Delley, J. Chem. Phy. 199, 92, 58. b) B. Delley, J. Chem. Phy. 2, 113, c) Dmol3 Moule, MS Moeling, Verion 2.2; Accelry Inc.: San, Diego, CA, 23. ) Male, J. R.; Hwang, M.-J.; Stockfich, T. P.; Dinur, U.; Walman, M.; Ewig, C. S.; Hagler, A. T. J. Comut. Chem. 1994, 15, 162. e) D. P. Yan, J. Lu, M. Wei, H. Li, J. Ma, F. Li, D. G. Evan, X. Duan, J. Phy. Chem. A 28, 112, f) D. P. Yan, J. Lu, M. Wei, J. B. Han, J. Ma, F. Li, D. G. Evan, X. Duan, Angew. Chem., Int. E., 29, 48, 373; g) J. P. Perew, J. A. Chevary, S. H. Voko, K. A. Jackon, M. R. Peeron, D. J. Singh, C. Fiolhai, Phy. Rev. B 1992, 46, 6671.