Transfer Hydrogenation of Cinnamaldehyde to

Cinnamyl alcohol in Hydrophobically Modified Core-

shell MOFs Nanoreactor: Identification of the formed

metal-N as ture active site

Haishuai Cui[a]†, Sihua Liu[b]†,Yang Lv[a], Shengtao Wu[a], Liping Wang[a], Fang

Hao[a,c], Pingle Liu[a,c,d]*,Wei Xiong[a,d]*, Hean Luo[a,c,d]

[a] College of Chemical Engineering, Xiangtan University, Xiangtan 411105, China

[b] College of Life Sciences and Chemistry, Hunan University of Technology,

Zhuzhou 412000, China

[c] Engineering Research Centre for Chemical Process Simulation and

Optimization of Ministry of Education, Xiangtan University, Xiangtan 411105,

China

[d] National & Local United Engineering Research Centre for Chemical Process Simulation and Intensification, Xiangtan University, Xiangtan 411105, China

Figure S1

Figure S1. Synthesis of ZIF-67, ZIF-8 and ZIF-Co:Zn.

Figure S2

Figure S2. XRD patterns of ZIF-67, ZIF-Co:Zn (2:1), ZIF-Co:Zn (1:1) and ZIF-8.

Figure S3

Figure S3. TGA curve of ZIF-67 (a), Deconvoluted Co 2p spectra for ZIF-67 (b), Deconvoluted

N1s spectra for ZIF-67(c), Deconvoluted O1s spectra for ZIF-67 (d).

Figure S4

Figure S4. XRD patterns of Fresh ZIF-67, undissolved ZIF-67 and precipitated solids.

Figure S5

Figure S5. XRD patterns of the Fresh ZIF-67 (a), ZIF-67@SiO2 (b), ZIF-67@SiO2-CPTEOS (c), precipitated solids of ZIF-67@SiO2 (d), precipitated solids of ZIF-67@SiO2-CPTEOS (e).

Figure S6

Figure S6. N2 adsorpton/desorption isotherms of ZIF-67 (black line), ZIF-67@SiO2-CPTEOS

(blue line) and the corresponding pore-size distribution curves of ZIF-67@SiO2-CPTEOS (pink

line).

Figure S7

Figure S7. SEM image of ZIF-67@SiO2-CPTEOS (a) and TEM image of ZIF-67@SiO2-CPTEOS

(b).

Figure S8

Figure S8. GC-(MS) spectra of the reaction products.

Table S1

Table S1. Basic parameters of tetrahedron (Co-N4) unit of ZIF-67

bond l0(Å) l0(Å)a angle θ0 (degrees) θ0 (degrees)a

Co-N 2.177 2.044 N-Co-N 105.4 109.3

N-C2 1.371 1.361 Co-N-C2 130.3 130.8

N-C1 1.365 1.377 Zn-N-C1 124.8 124.7

C1-C1 1.395 1.375 C1-N-C2 104.8 104.4

C1-H1 1.084 1.077 C1-C1-N 107.8 107.9

C2-C3 1.483 1.498 C1-C1-H1 130.7 130.6

C3-H2 1.096 1.091 C2-C3-H2 109.7 110.8

a The basic parameters of tetrahedron (Co-N4) unit of ZIF-67 in the literature.

Table S2

Erel r(Co-Oa) r(Co-Ob) r(Ca-Oa) r(Ca-Hc) r(Ob-Ha) r(Co-N1)

A1 -64.932 1.958 2.137 1.262 1.098 0.987 1.987

A2 -63.025 1.972 2.086 1.260 1.099 0.992 1.994

A3 -64.438 4.276 2.034 1.235 1.114 0.992 1.929

A4 -59.813 4.399 2.018 1.246 1.113 0.999 1.902

A5 -57.289 1.946 4.633 1.258 1.105 0.988 1.939

A6 -68.229 1.947 5.586 1.264 1.106 0.999 1.903

A7 -57.122 5.290 2.101 1.233 1.116 0.985 1.932

D1 -63.576 1.994 1.833 1.257 1.110 3.547 4.153

TABLE S2. Relative energies (Kcal/mol),a optimized bond lengths (Å) in the different adsorption complexes depicted in Chart 1.

a Calculated with respect to the sum of the energies of CAL + isopropanol + the Co-N4 cluster model.

Table S3

TABLE S3. Optimized distances (in Å) and relative energies (Kcal/mol)a of the transition states depicted in Chart 2

Erel r(Co-Oa) r(Co-Ob) r(Ca-Oa) r(Cb-Hb) r(Ob-Ha) r(Co-N1) r(Ca-Hb)

TS1

-62.7098 1.987 1.849 1.259 1.113 2.395 4.111 4.570

TS2

-55.4580 1.975 2.017 1.268 3.394 3.450 2.021 3.899

TS3

-52.0958 5.117 1.995 1.235 4.471 4.519 1.957 3.655

TS4

-56.4056 1.944 6.370 1.259 6.121 4.054 1.942 4.652

TS5

-58.7085 2.043 1.979 1.296 3.500 3.308 4.050 2.276

a Calculated with respect to the sum of the energies of CAL + isopropanol + the Co-N4 cluster model.

Chart S1