nl4c00512_si_001 (1)

Download as pdf or txt
Download as pdf or txt
You are on page 1of 39

Supporting information

Zn-single Atom Catalysts Enable the Catalytic Transfer


Hydrogenation of α, β-Unsaturated Aldehydes

Jiawen Chen,† Yongming Xia,‡ Yuxuan Ling,† Xuehui Liu,† Shuyuan Li,‡ Xiong Yin,*,†
Lipeng Zhang,‡ Minghui Liang,§ Yi-Ming Yan,‡ Qiang Zheng,§ Wenxing Chen,∥Yan-
Jun Guo,§ En-Hui Yuan,⊥ Gaofei Hu,† Xiaole Zhou,† and Leyu Wang*,†


State Key Laboratory of Chemical Resource Engineering, Innovation Centre for Soft
Matter Science and Engineering, College of Chemistry, Beijing University of Chemical
Technology, Beijing 100029, China.

State Key Laboratory of Organic-Inorganic Composites, College of Chemical
Engineering, Beijing University of Chemical Technology, Beijing 100029, China.
§
CAS Key Laboratory of Standardization and Measurement for Nanotechnology, CAS
Key Laboratory of Nanosystem and Hierarchical Fabrication, National Center for
Nanoscience and Technology, Beijing 100190, China.

Energy and Catalysis Center, School of Materials Science and Engineering, Beijing
Institute of Technology, Beijing 100081, China

School of Chemistry & Chemical Engineering, Shaanxi Normal University, Xi’an
710119, China

*Corresponding authors:

[email protected] (Xiong Yin); [email protected] (Leyu Wang)

s1
Experimental

Preparation of zeolitic imidazolate framework-8 (ZIF-8), Zn/NC-T, Zn/NC-900-


acid and ZnO samples

Briefly, 1.190 g Zn(NO3)2·6H2O was dissolved in methanol and stirred for 10 min, and

then it was quickly added into another methanol containing 1.314 g of 2-

methylimidazole (MeIM). The mixture was stirred for 4 h at room temperature. After

that, nanoparticles (ZIF-8) were obtained in the container. The as-obtained ZIF-8

particles were centrifuged and washed with methanol three times. Finally, the sample

was vacuum-dried at 60 °C overnight and kept for usage. The as-obtained ZIF-8

samples were placed in a porcelain boat. It was then sintered at certain calcination

temperatures for 1 h under an N2 atmosphere with a heating rate of 5°C /min. The

calcination temperature was set at 700°C, 800°C, 900°C, and 1000°C, respectively.

Thus, the corresponding collected samples were named Zn/NC-700, Zn/NC-800,

Zn/NC-900, and Zn/NC-1000, respectively. In the case of the preparation of Zn/NC-

900-acid catalyst, the Zn/NC-900 (100 mg) sample was immersed into the aqueous

solution of HCl (0.5 mol/L, 10 mL). Then, they were stirred at 80 °C for 5 h. After that,

the solid sample was washed using deionized water to remove the residual acid. The

pH of the final solution was controlled to be about 7.0. The Zn species contained in the

Zn/NC-900-acid catalyst was 2.6 wt.%, measured by ICP. In addition, as for the

synthesis of the ZnO sample, the as-obtained ZIF-8 precursors were placed in a ceramic

boat, and they were sintered in a muff furnace at 400 °C for 1 h under ambient

atmosphere with a rate of 5 °C /min. After cooling to room temperature, the ceramic

boat was transferred to a tube furnace, and then, they were sintered at 900°C for 1 h

under a N2 atmosphere with a rate of 5 °C /min. Finally, a powder of light-yellow color

was obtained.
s2
Selective hydrogenation reactions

Selective hydrogenation reactions of cinnamaldehyde (CAL) were conducted in a 50

ml round bottom flask, which was loaded with 60 mg of catalyst, 49 mg of CAL, and

35 mL of isopropyl alcohol (IPA). A spherical condenser tube was connected to the

flask. Prior to running the reaction, the system was evacuated with double-row tube

equipment, and then filled with nitrogen, and the evacuated cycle was repeated at least

three times. Finally, a nitrogen-filled balloon was equipped over the condenser tube to

keep the N2 atmosphere. After that, the reaction system was heated to the reaction

temperature (80 °C) with a stirring speed of 600 rpm. Five hours later, the liquid mixture

was separated from the solid catalyst by filtration method. The final products were

analyzed using an Agilent 7890B gas chromatograph (GC) equipped with an FFAP

capillary column, an auto-injector, and a flame ionization detector (FID). The mass

fragmentation analysis of products for IPA-d8 and TBA was conducted on a gas

chromatography-mass spectrometry (GC-MS, Agilent 7200 Q-TOF) with a DB-1701

capillary column. The conversion of CAL and selectivity of COL were obtained

according to the following equations (1 and 2)1:

Conversion of CAL (%) =

moles of CAL before reaction−moles of CAL after reaction


× 100% (1)
moles of CAL before reaction

moles of Production
Selectivity of COL (%) = moles of CAL consumed × 100% (2)

In the case of the hot filtration experiment, the catalytic transfer hydrogenation

reaction between CAL and IPA catalyzed by Zn/NC-900 catalyst was suspended after

they were heated for 30 min. Then, the catalyst was removed from the reaction solution

by the filtration method. The supernatant was allowed to be stirred for an additional

11.5 hours under the same reaction conditions. The conversion of CAL and selectivity
s3
of COL at 0.5 h and 12 h were checked using a GC approach, respectively. Furthermore,

as for the poisoning acid- and base-sites experiments, excess of KSCN and HCOOH

was added into the reaction solution, respectively.

Isopropanol-D1 [CH3CH(OD)CH3], and the mixture of isopropanol-D8

[CD3CD(OD)CD3] and tert-butanol with a volume ratio of 1:3 were used as solvents

for the CTH reactions to confirm the reaction mechanism2-3. It should be noted that in

the mixed solvents, the tert-butanol can exchange H with D in the isopropanol-D8 to

yield CD3CD(OH)CD34. The mass fragmentation analysis of final products was further

conducted using a GC-MS (Agilent 7200 Q-TOF, with a DB-1701 capillary column)

Stability test of Zn-based SACs toward catalytic transfer hydrogenation

In the case of the stability test of Zn-N-C SACs, the reaction solution was filtered

after each run, and the catalyst was washed using IPA to remove the organic molecules

adsorbed on the surface of the catalysts. Finally, the catalysts were dried in a drying

oven overnight. Prior to the next cycle of the catalysis test, the catalyst was heated at

400 °C for 1 h under a N2 atmosphere with a heating rate of 5°C/min to remove the

organic chemicals, which were strongly adsorbed at the active sites of the catalysts. A

certain amount of CAL was added into the three-neck round flask according to the mass

ratio between the Zn species of Zn-SAC and CAL used in the 1st run. The catalytic

reaction was conducted under the same conditions as those for the 1st run.

CTH reactions of α, β-unsaturated aldehydes

The CTH reactions for various α, β-unsaturated aldehydes catalyzed by the Zn/NC-

900 catalyst were also investigated. The reactions were conducted for a certain time at

several temperatures, and those products were quantified by GC or 1HNMR. Typically,

hexanol, benzyl alcohol, and cyclohexanol were used as the hydrogen donor for the

s4
transfer hydrogenation reaction of cinnamaldehyde. Those reactions were carried out at

140 °C for 11 hours. In addition, in the case of 3-methyl-2-butenal (31 mg) as the

reactant, the mass of the catalyst was 100 mg, and the reaction was run at 80 °C for 11

h. Moreover, the reactions of 3-methyl-2-butena, furfural, α-methylcinnamaldehyde

and various alcohols containing β-H as hydrogen sources were quantified using the GC

method. The products for IPA and 4-nitrocinnamaldehyde, 4-methoxycinnamaldehyde,

α-amylcinnamaldehyde and 5-hydroxymethylfurfural were quantified by 1HNMR

technique, with trimethoxybenzene as the internal standard substance.

Characterization

The morphologies and sizes of the as-prepared Zn/NC-T catalysts were characterized

with a JEM-1200EX (JEOL) TEM operated at 100 kV. Electron energy loss spectra

(EELS) of the samples were recorded by using a Tecnai G2 F20 UTWIN TEM equipped

with a field emission gun. High-angle annular dark field (HAADF) scanning

transmission electron microscopy (STEM) characterizations were performed with a

spherical aberration-corrected instrument (FEI-Themis Z) operated at 200 kV. The

Powder X-ray diffraction (XRD) patterns were recorded on a Bruker AXS D8 Advance

X-ray diffractometer with Cu Kα radiation. The contents of Zn species contained in the

Zn/NC-T catalysts were determined by an inductively coupled plasma atomic emission

spectrometer (ICP-OES, Thermo Fisher ICAP-6300). Prior to the measurement, all

samples were dissolved in the aqua regia for the nitration process, and the solutions

were diluted to a certain concentration for testing. Characterization of the catalysts by

the Brunauer-Emmett-Teller (BET) method was carried out on an ASAP 2460

instrument. The X-ray photoelectron spectroscopy (XPS) was carried out on a Thermo

Scientific K-Alpha photoelectron spectrometer. The X-ray absorption spectra (XAS) of

s5
the Zn K-edge were measured at the 1W1B station of the Beijing Synchrotron Radiation

Facility (BSRF, 2.5 GeV, 250 mA, monochromatized with Si (111) double-crystals).

Moreover, the N K-edge of the Zn/NC-900 sample was collected at the Beijing

Synchrotron Radiation Facility (BSRF) line 4B9B station. Temperature programmed

desorption of ammonia (NH3-TPD) was conducted on the Micromeritics AutoChem II

2920 instrument. Typically, each sample (50 mg) was pretreated in flowing of He for 1

h at 300 °C. Then, it was cooled down to 80 °C under He atmosphere, and saturated

with 10% NH3/He. After that, the sample was purged with He for 2 h to eliminate the

physically adsorbed NH3. Finally, NH3-TPD profiles were collected in flowing He in

the temperature range of 50 ~ 500 °C with a heating rate of 10 °C/min.

The FT-IR spectra of substrates chemically absorbed on the catalysts were collected

on an integrated FOLI 20-Z Fourier transform infrared spectrometer equipped with a

VeeMAX III specular reflection attachment. The catalysts were first mixed with

anhydrous ethanol and naphthol solution to form a slurry, which was repeatedly coated

on the glass carbon electrode in a small amount, and the electrode was dried under an

infrared lamp. Then, the corresponding substrate or their mixtures were dropped onto

the glass carbon electrode which was coated by different catalysts, respectively. Prior

to the measurement, the electrodes coated with catalysts adsorbed by substrates were

purged for a while using an inert gas with the aim of removing the physically adsorbed

substrates on the catalysts surface. Finally, the signals were collected at a certain time

interval under the atmosphere of inert gas for each catalyst and substrate. As for the

reference signals, the different substrate or their mixtures on the glassy carbon electrode

were also measured according to the same procedure. In situ FT-IR experiments were

conducted on a Bruker TENSOR 27 equipped with an MCT narrow-band detector and

a self-made temperature-controlled gas-liquid-solid reaction cell (Beijing Scistar


s6
Technology Co. Ltd.). The reactants in the system were diluent in an equal proportion

using tetrachloroethylene. Prior to running the reaction, the deduction of background

absorption was performed. The reaction temperature of system increased gradually via

heating. When it reached the reaction temperature, the IR signals of reactants and

products were collected at various reaction times.

DFT calculations

All first-principles calculations were performed using the Vienna Ab-initio

Simulation Package (VASP)5-6. The exchange-correlation energy was approximated by

the generalized gradient approximation (GGA) of Perdew-Burke-Ernzerhof (PBE)

functional7-8. Spin polarization as well as vdW-dispersion energy-correction of DFT-

D3 were considered9-10. A periodically projected plane wave basis set was employed

using the projector-augmented wave (PAW) method with a kinetic energy cutoff of 500

eV, and with a Monkhorst-Pack k-point grid of 3 × 3 × 1 for the Brillouin zone sampling

for structural optimization. The convergence criterion for the self-consistent iteration

was 1×10-4 eV. The ionic relaxations can be terminated when the force on each atom is

less than 0.02 eV/Å. The single-atom catalyst model is built based on a graphene

structure containing Zn-N moiety with lattice dimensions of 17.04 × 19.68 Å in the

basal plane and 15 Å in a perpendicular direction to ensure a sufficiently large vacuum.

This system size is found to be sufficiently large to eliminate the interaction energies

between the neighboring metals due to periodical structure. The formation energy of

the model catalyst was calculated as:


y
Ef = EM-N-C + xEC - Egra - 2 EN2 - EM (3)

Where Ef represents the formation energy. EM-N-C and Egra represent the energy of

the optimized M-N-C catalyst and graphene, respectively. EC refers to the energy of a

s7
single carbon atom in graphene, and x represents the number of C atoms;

EN2 represents the energy of nitrogen, y represents the number of N atoms. EM

represents the energy of a single metal atom in metal bulk. The adsorption energy was

calculated as

ΔG = Gtotal - Ggra - Gmolule (4)

Where Gtotal represents the total energy of the whole system when the reaction

intermediates are adsorbed at the active site. Ggra represents the energy of the initial

catalyst without adsorbing intermediates. Gmolule represents the energy of the

intermediate of the reaction.

s8
Figure S1. Schematic diagram for the synthesis of Zn-N-C single-atom catalysts
(SACs).

Zn single-atom catalysts (Zn-SACs) were prepared via a facile “self-template and


pyrolysis” strategy (Figure S1). The self-template, ZIF-8 nanoparticle (NP), was
prepared by mixing the zinc nitrate hexahydrate and 2-methylimidazole in a methanol
solution at room temperature for 4 h. The as-prepared ZIF-8 NPs were then subjected
to pyrolysis under an N2 atmosphere at certain temperatures for 1 h to yield Zn-based
catalysts. Especially, Zn-based catalysts prepared at 700, 800, 900 and 1000 ºC were
labeled as Zn/NC-700, Zn/NC-800, Zn/NC-900 and Zn/NC-1000, respectively. During
the pyrolysis, the organic components of ZIF-8 were transformed into a nitrogen-doped
carbon (N-C) matrix, and most Zn species were sublimated simultaneously.

s9
Table S1. The contents of Zn, N, C and O species contained in various Zn-based
catalysts measured by ICP-MS and XPS.

Zn / wt.% Zn / wt.% N / wt.% C / wt.% O / wt.%


Catalysts
(ICP) (XPS) (XPS) (XPS) (XPS)
Zn/NC-700 24.3 20.0 15.1 53.8 11.1
Zn/NC-800 14.6 18.2 14.3 54.2 13.3
Zn/NC-900 12.0 10.9 11.3 68.3 9.5
Zn/NC-1000 5.7 6.2 7.0 76.8 10.0

The calcination temperature could influence the loading amount of Zn species in the
final Zn-based catalysts. Higher calcination temperature led to a lower loading amount
of Zn species, revealed by the inductively coupled plasma atomic emission
spectroscopy (ICP-AES, Table S1). Typically, the loading amount of Zn species
maintained 12.0 wt.% in the Zn/NC-900 sample, however, it changed to 5.7 wt.% for
the Zn/NC-1000 sample.

s10
Figure S2. TEM images of Zn/NC catalysts prepared at different calcination
temperatures: (a) Zn/NC-700; (b) Zn/NC-800; (c) Zn/NC-900; (d) Zn/NC-1000, and (e)
recycled Zn/NC-900 catalyst.

All Zn/NC samples retained the dodecahedral morphologies, which are similar to
those of ZIF-8, and no obvious aggregations of nanoparticles were observed on the
surface of the samples (Figure S2).

s11
Figure S3. XRD patterns of Zn/NC catalysts prepared at different calcination
temperatures.

Two broad peaks around 24° and 43° could be observed from the X-ray diffraction
(XRD) patterns (Figure S3), in response to (002) and (101) planes of amorphous carbon
materials, respectively. No peaks stemmed from zinc oxides and Zn particles were
observed, suggesting a good dispersion of Zn species within the N-C matrix.

s12
Figure S4. XPS spectra of Zn/NC-900 single atom catalyst: (a) Zn 2p; (b) N 1s; (c) C
1s; (d) O 1s.

X-ray photoelectron spectroscopy (XPS) was further utilized to characterize the


valence states and compositions of Zn/NC samples. Two typical binding energies for
Zn 2p, 1021.9 eV (Zn 2p3/2) and 1044.9 eV (Zn 2p1/2), were present in the Zn/NC-900
SAC, indicating that Zn species existed in the positive valence state in the Zn/NC-900
SAC sample (Figure S4a). A peak at 398.8 eV associated with the Zn-N bond was also
found (Figure S4b).

s13
Figure S5. The XPS spectra for N 1s in the reference NC-900, and various Zn/NC
samples prepared at different calcination temperatures.

Compared to the reference nitrogen-doped carbon sample (NC-900), four Zn/NC


samples had the extra Zn-N peak (Figure S5). Simultaneously, the N atoms were
embedded well within the carbon support, verified by the C1s XPS (285.2 eV for C-N,
Figure S4c), and no peak from the Zn-O bond was observed in the O1s XPS (Figure
S4d).

s14
Figure S6. The N2 adsorption–desorption isotherms of Zn/NC catalysts prepared at
different calcination temperatures: (a) Zn/NC-700; (b) Zn/NC-800; (c) Zn/NC-900; and
(d) Zn/NC-1000.

s15
Figure S7. The pore size profile of Zn/NC catalysts prepared at different calcination
temperatures: (a) Zn/NC-700; (b) Zn/NC-800; (c) Zn/NC-900; and (d) Zn/NC-1000.

As revealed by Brunauer–Emmett–Teller (BET) analysis (Figure S6), the as-


prepared Zn/NC samples inherited the high surface area and abundant porosity, and
they held the microporous structures (Figure S7), which are beneficial for the mass
transfer of substrates during the catalytic process.

s16
Figure S8. N K-edge XANES spectra of Zn/NC-900 catalyst and reference N-C sample.

s17
Table S2. EXAFS fitting parameters at the Zn K-edge for Zn/NC samples (Ѕ02= 0.84).

Sample Path C. N.a R (Å)b σ2×103 (Å2)c ΔE (eV)d R factor

Zn-Zn 6* 2.65±0.01 9.8±0.7


Zn foil 1.1±1.3 0.002
*
Zn-Zn 6 2.78±0.03 20.4±2.7

Zn-O 3.7±0.6 1.97±0.01 4.1±1.6 4.4±2.0


ZnO 0.014
Zn-Zn 10.4±1.9 3.23±0.01 12.8±1.4 2.6±1.5

Zn-N 4.1±0.5 1.99±0.01 3.2±0.9 10.7±1.7


ZnPc 0.012
Zn-C 5.7±1.8 2.99±0.02 2.3±2.0 11.1±2.3

Zn-N/C1 3.2±0.3 1.86±0.01 5.7±0.6 1.0±0.2


Zn/NC-700 0.007
Zn-N/C2 3.9±0.5 1.96±0.01 6.5±0.8 1.0±0.2

Zn/NC-800 Zn-N/C 4.1±0.6 1.96±0.01 4.1±0.5 1.0±0.2 0.006

Zn/NC-900 Zn-N/C 3.2±0.5 1.95±0.01 3.8±0.5 1.0±0.2 0.005

Zn/NC-1000 Zn-N/C 2.9±0.5 1.96±0.01 4.8±0.5 1.0±0.2 0.007

Zn/NC-900-used Zn-N/C 3.1±0.5 1.96±0.01 5.1±0.5 1.0±0.2 0.006

S02 is the amplitude reduction factor; aC.N: coordination numbers; bR: bond distance;
c 2
σ : Debye-Waller factors; dΔE: edge-energy shift. R factor: goodness of fit. *: fitting
with fixed parameter.

s18
Figure S9. Optimization of the reaction conditions for the CTH reaction between CAL
and alcohol: (a) solvent; (b) reaction time; and (c) reaction temperature.

Different types of alcohols as reactants, including methanol, ethanol, isopropanol (IPA)


and tert-butanol (TBA) were evaluated for the CTH reaction (Figure S9a). The IPA
showed the highest reactivity and selectivity toward COL. However, in the case of TBA,
its selectivity to COL was very low, suggesting that the β-H in the reactant alcohol was
indispensable to the CTH reaction.

s19
Figure S10. (a) Hot filtration test of CTH reaction between CAL and IPA; (b) stability
evaluation of Zn/NC-900 catalyst towards selective transfer hydrogenation of CAL and
IPA. Reaction conditions: 60 mg of Zn/NC-900 catalyst, 80 °C, 5 h, 49 mg of CAL.

s20
Table S3. Catalytic transfer hydrogenation reactions of various α, β-unsaturated
aldehydes with different alcohols over the Zn/NC-900 catalyst.

Entry Conversion/ Selectivity/


Substrate Alcohol Product
No. % %

1a 94.0 97.3

2a 93.3 98.1

3a 99.9 99.9

4a 89.6 83

5b 96.6 90.2

6a 99.4 88.7

7a 99.7 96.1

93.7
8c 93.3

9c 96.7 92.1

10c 90.3 81.7

a
The molar ratio between reactant and Zn specie of catalyst was 6:1
b
Reaction condition: 31 mg of substrate, 100 mg of catalyst (Zn/NC-900), 35 mL of
IPA, 0.1MPa N2, reaction temperature: 80 °C; reaction time: 11 hours
c
Reaction condition: 48 mg of cinnamaldehyde, 60 mg of catalyst (Zn/NC-900), 5 mL
of solvent, 0.1MPa N2, reaction temperature: 140 °C, reaction time: 11 hours

s21
When the cinnamaldehydes substituted by electron-donating, electron-withdrawing,
and spatial resistance groups were used as reactants (Figure 2c, entries 1-4, Table S3),
the corresponding desirable products (their 1HNMR shown in Figures S11-14) were
obtained in relatively high yields (89.6-99.9%). In the case of 3-methyl-2-butenal, the
conversion and selectivity were over 90% (Figure 2c, entry 5). More importantly, 2-
furaldehyde and its derivate could also undergo a CTH reaction to produce furfuryl
alcohol and 2, 5-furandimethanol, exhibiting high both yields and selectivity (Figure
2c, entries 6, 7). Besides IPA, the alcohols containing the β-H group, i.e. benzyl alcohol,
cyclohexanol, and hexyl alcohol could effectively transfer hydrogen to CAL to yield
COL with high conversion (90-96%) and selectivity (81-94%) (Figure 2c, entries 8, 9,
10, Table S3). Therefore, the Zn-SAC with Zn-N3 moieties displayed superior catalytic
performance toward CTH.

s22
Figure S11. 1H NMR spectrum for the product of Entry No. 2 summarized in Table S3.
1
H frequency was 400.13 MHz, and the sample was dissolved in DMSO-d6. * refers to
the residual proton signal of DMSO (δ 2.5) and HDO (δ 3.3) in the deuterated solvent.

1
H NMR (400 MHz, DMSO-d6) δ 7.35 – 7.19 (m, 5H), 6.47 (s, 1H), 4.93 (t, J = 5.7 Hz,
1H), 4.02 (d, J = 5.6 Hz, 2H), 2.19 (t, J = 8.1 Hz, 2H), 1.49 – 1.41 (m, 2H), 1.25 (m, J
= 7.3, 5.8, 2.6 Hz, 4H), 0.93 – 0.80 (t, J = 7.3, 3H).

s23
Figure S12. 1H NMR spectrum for the product of Entry No. 3 summarized in Table S3.
1
H frequency was 400.13 MHz, and the sample was dissolved in DMSO-d6. * refers to
the residual proton signal of DMSO (δ 2.5) and HDO (δ 3.3) in the deuterated solvent.
1
H NMR (400 MHz, DMSO-d6) δ 8.20 – 8.10 (m, 2H), 7.72 – 7.65 (m, 2H), 6.77 – 6.62
(m, 2H), 5.05 (t, J = 5.4 Hz, 1H), 4.19 (dd, J = 5.4, 3.0 Hz, 2H).

s24
Figure S13. 1H NMR spectrum for the product of Entry No. 4 summarized in Table S3.
1
H frequency was 400.13 MHz, and the sample was dissolved in DMSO-d6. * refers to
the residual proton signal of DMSO (δ 2.5) and HDO (δ 3.3) in the deuterated solvent.

1
H NMR (400 MHz, DMSO-d6) δ 7.39 – 7.31 (m, 2H), 6.93 – 6.80 (m, 2H), 6.49 (d, J
= 15.9 Hz, 1H), 6.22 (dt, J = 15.9, 5.3 Hz, 1H), 4.81 (t, J = 5.5 Hz, 1H), 4.10 (m, 2H),
3.75 (s, 3H).

s25
Figure S14. 1H NMR spectrum for the product of Entry No. 7 summarized in Table S3.
1
H frequency was 400.13 MHz, and the sample was dissolved in DMSO-d6. * refers to
the residual proton signal of DMSO (δ 2.5) and HDO (δ 3.3) in the deuterated solvent.
1
H NMR (400 MHz, DMSO-d6) δ 6.19 (s, 2H), 5.17 (t, J = 5.7 Hz, 2H), 4.36 (d, J = 5.7
Hz, 4H).

s26
Table S4. Various catalysts for CTH reaction of different α, β-unsaturated aldehydes
with alcohols reported in the literatures.

Conv. Sel. Reaction


Catalysts Substrate Product H donor Reference
/% /% condition
ISAS- toluene, Angew. Chem. Int.
99 99 120 °C, 1.5h HCOOH Ed. 2018, 57,
Co/OPNC 0.1 MPa 11262
60 °C, 8h,
Nat. Commun.
Pd1/ND@G 100 98 MeOH NH3BH3
2021, 12, 6194
sealed tube
Ru-CTF-I-900
140 °C, 24h Adv. Sci., 2021, 8,
(single atoms 100 99 IPA
autoclave 2001493
and clusters)

130 °C, 3h, J. Mater. Chem. A


Ni-SAs/NC 95.6 96.8 IPA
2MPa N2 2021, 9, 1110

130 °C, 2.5h Green Chem.


Zr1/NC ~100 ~100 IPA
autoclave 2022, 24, 6931

Cu1@UiO-66- 140 °C, Chem. Eng. J.


100 96.7 1MPa N2, IPA 2023, 454,
(COOH)2 10h 140156

Zn(OTf)2/ Hantzsch Chem. Asian. J.


~90 / 60~80 °C
Chiral ligand Ester 2012, 7, 2562

CoOx@Co 120 °C, 8h, ChemCatChem


97.5 90.1 IPA
NPs 0.1MPa N2 2020, 12, 1019

Zr-BDB 100 °C, 6h


Green Chem.
96.9 97.2 stainless IPA
nanoparticles 2021, 23, 1259
reactor

Zr-tannin 80 °C, 4h
Green Chem.
95 97 pressure IPA
nanoparticles 2020, 22, 180
tube

ZIF-67@SiO2- 180 °C, 12h, J. Catal. 2020,


84.59 95.01 IPA
CPTEOS 1MPa N2 381, 468

ACS Appl. Nano


150 °C, 12h,
Pt NP/UiO-66 90.5 94.6 IPA Mater. 2020, 3,
1MPa N2
12260

Ni-SAs/ 150 °C, 2h, J. Catal. 2021,


100 100 IPA
MgAlO-450 1MPa N2 393, 1

Zn/NC-900 80 °C, 5h,


95.4 95.5 IPA This work
ZnN3 SAC 0.1MPa N2

Zn/NC-800 80 °C, 5h,


85.9 84.4 IPA This work
ZnN4 SAC 0.1MPa N2

s27
Figure S15. Chromatogram of final compositions for the isopropanol dehydrogenation
experiment by GC with a TCD detector.

To elucidate the mechanism, a controlled experiment, the dehydrogenation of


isopropanol in the Zn/NC-900-added isopropanol system was first conducted. As
shown in Figure S15, the gas chromatography (GC) with a thermal conductivity
detector (TCD) analysis revealed that no H2 was observed in the final product. The
results indicated that the possibility of H2 formation from the dissociated isopropanol
as the hydrogen source was extremely low in our study.

s28
Figure S16. 1HNMR of the products for the CTH reaction between CAL and IPA-d1
(CH3CH(OD)CH3)

s29
Figure S17. Scheme of the reaction mechanism for CTH reaction via direct hydrogen
transfer route (Meerwein-Ponndorf-Verley, MPV mechanism, Path A) and metal
hydride route (Path B).

s30
Figure S18. 1HNMR for the deuteration experiments over catalysts Zn/NC-800 (a) and
Zn/NC-900 (b), using the mixture of IPA-d8 [CD3CD(OD)CD3] and TBA with volume
ratio of 1:3 as solvent.

s31
Figure S19. Mass fragmentation analysis of the products for the CTH reaction between
CAL and mixed solvents of IPA-d8 and TBA (volume ratio of 1:3) catalyzed by Zn/NC-
900 SACs.

Furthermore, the isotopically labeled IPA-d1 (C3H7OD) was chosen as a reactant to


investigate the hydrogen transfer process of the CTH reaction. The corresponding
product was COL-d1 (C9H9OD), verified by HNMR (Figure S16). It implied that the D
atom of the OD group in the IPA-d1 (C3H7OD) reacted with the O atom of C=O in CAL
to yield the C-OD group. Simultaneously, the β–H of IPA-d1 transferred and attacked
the C site of C=O in COL, and thus, COL-d1 (C9H9OD) and acetone were generated
accordingly. Two possible reaction pathways for the CTH reaction have been proposed,
including direct transfer pathway (Meerwein-Ponndorf-Verley mechanism, Path A) and
metal hydride formation pathway (Path B), as shown in Figure S17.11,12 Subsequently,
to clarify the reaction pathway of CTH over the as-developed Zn-N-C SACs, the mixed
solvent of TBA and IPA-d8 with a volume ratio of 3:1 was used as the hydrogen donor.
In the mixture, TBA could easily exchange H atoms with IPA-d8 to produce C3D7OH,13
and the resultant C3D7OH reacts with CAL accordingly. The COL-d1 (C9H9OD) would
be the main product if the CTH reaction proceeded via Path A (MPV mechanism, Figure
S17a). Otherwise, the COL was the main product when the CTH reaction proceeded
via Path B. In the case of path B, there exists an exchanging step between the OH group
of TBA and D atoms located on the surface of catalysts, which would result in the
formation of COL (Figure S17b). Revealed by 1HNMR (Figure S18), the ratio between
COL-d1 and COL was 9:1 in the final products catalyzed by the Zn-N3 and Zn-N4 SACs.
Furthermore, the formation of COL-d1 and COL was also confirmed by MS (Figure
S19). It can be concluded that the CTH reaction between CAL and IPA catalyzed by the
as-developed Zn-N-C SACs mainly proceeded via the MPV mechanism (Path A) in the
study.

s32
Figure S20. FT-IR spectra of isopropanol and cinnamaldehyde chemisorbed on the
Zn/NC-900 SAC (a, b), and NC-900 (c, d) catalysts, respectively.
The adsorption behaviors of reactants were then monitored by FT infrared
spectroscopy. As for IPA, a peak (1153.5 cm−1) attributed to the νC−O was observed
(Figure S20a). The peak of νC−O presented a red shift from 1153.5 to 1146.5 cm−1 on
the Zn/NC-900 catalyst, and the wavenumber of other peaks changed negligibly.14 The
red shift of νC−O could be attributed to the adsorption of the C−O group of the IPA over
the Zn/NC-900. Additionally, in the case of CAL, its typical peak for νC=O at 1676 cm−1
also shifted to 1673.6 cm−1 when it was absorbed on the Zn/NC-900 (Figure S20b),
indicating that the C=O of CAL interacted with the catalyst.15,16 More importantly, a
larger red shift was observed when IPA and CAL were located simultaneously on the
Zn/NC-900 catalyst, suggesting that the two reactants were co-adsorbed on the same
Zn sites. Nevertheless, as for the control NC-900 catalyst, no shifts of those peaks were
observed (Figures S20c, d), implying that neither IPA nor CAL was absorbed on the
NC-900 catalyst. Thus, it can be expected that the D atom in the COL-d1 (C9H9OD)
originated from IPA-d1 (C3H7OD) via the direct transfer pathway (MPV mechanism,
path A) (Figure S17), in which the β–H of COL-d1 directly transferred from the β–H of
IPA-d1.

s33
Table S5. The formation energy for ZnN4 coordination configuration with different
numbers of pyridinic-N and pyrrolic-N species.

Formation
No. Coordination Structure
energy/eV

1 Zn-4Npyridine -6.185

2 Zn-3Npyridine-1Npyrrole -3.80

3 Zn-2Npyridine-2Npyrrole-1 -5.92

4 Zn-2Npyridine-2Npyrrole-2 -1.30

5 Zn-1Npyridine-3Npyrrole -2.99

6 Zn-4Npyrrole -4.197

s34
Table S6. The formation energy for ZnN3 coordination configuration with different
numbers of pyridinic-N and pyrrolic-N species.

Formation
No. Coordination Structure
energy/eV

1 Zn-3Npyridine -1.75

2 Zn-2Npyridine-1Npyrrole -0.39

3 Zn-1Npyridine-2Npyrrole-1 1.73

4 Zn-1Npyridine-2Npyrrole-2 3.93

5 Zn-3Npyrrole -0.13

s35
Table S7. The formation energy and adsorption configuration of isopropanol and
cinnamaldehyde over the ZnN4 SACs.

Adsorption Structure Adsorption


No. Substrate
site Initial state Final state energy/eV

C -0.067

N /
1 Isopropanol
Zn -0.087

Zn -0.063

C -0.215

N /

2 Cinnamaldehyde
Zn -0.37

Zn -0.078

s36
Table S8. The formation energy and adsorption configuration of isopropanol and
cinnamaldehyde over the ZnN3-SACs.

Adsorption Structures Adsorption


No. Substrate
site Initial state Final state energy/eV

C -1.433

1 Isopropanol
N -1.436

Zn -2.033

C -2.038

N -

2 Cinnamaldehyde
Zn -1.913

Zn -2.053

s37
References:
[1] Zhang, Y., Yan, J., You, R., He, M., Wang, L., Liang, M. The effect of the interaction
between Cu single atoms and Pt nanoparticles on the selective hydrogenation of
epichlorohydrin to chloro-propanol. Appl. Surf. Sci. 628, 157382 (2023).
[2] Valekar, A., Lee, M., Yoon, J., Kwak, J., Hong, D.-Y., Oh, K., Cha, G.-Y., Kwon,
Y.-U., Jung, J., Chang, J., Hwang, Y. Catalytic Transfer hydrogenation of furfural to
furfuryl alcohol under mild conditions over Zr-MOFs: exploring the role of metal node
coordination and modification. ACS Catal. 10, 3720–3732 (2020).
[3] Gilkey, M., Panagiotopoulou, P., Mironenko, A., Jenness, G., Vlachos, D., Xu, B.
Mechanistic insights into metal-lewis acid mediated catalytic transfer hydrogenation of
furfural to 2-Methylfuran. ACS Catal. 5, 3988-3994 (2015).
[4] Berkessel, A., Schubert, T., Müller, T., Hydrogenation without a transition-metal
catalyst: on the mechanism of the base-catalyzed hydrogenation of ketones. J. Am.
Chem. Soc. 124, 8693-8698 (2002).
[5] Kresse, G., Furthmüller, J. Efficiency of ab-initio total energy calculations for
metals and semiconductors using a plane-wave basis set. Comput. Mater. Sci. 6, 15-50
(1996).
[6] Kresse, G., Furthmüller, J. Efficient iterative schemes for ab initio total-energy
calculations using a plane-wave basis set. Phys. Rev. B. 54, 11169 (1996).
[7] Perdew, J., Burke, K., Ernzerhof, M., Generalized gradient approximation made
Simple. Phys. Rev. Lett. 77, 3865-3868 (1996).
[8] Solovyev, I., Dederichs, P., Anisimov, V. Corrected atomic limit in the local-density
approximation and the electronic structure of D impurities in Rb. Phys. Rev. B. 50,
16861-16871 (1994).
[9] Grimme, S. Semiempirical gga-type density functional constructed with a long-
range dispersion correction. J Comput Chem. 27, 1787-1799 (2010).
[10] Grimme, S.; Antony, J., Ehrlich, S., Krieg, H. A consistent and accurate ab initio
parametrization of density functional dispersion correction (Dft-D) for the 94 elements
H-Pu. J. Chem. Phys. 132, 154104 (2010).
[11] Valekar, A.; Lee, M.; Yoon, J.; Kwak, J.; Hong, D.-Y.; Oh, K.; Cha, G.-Y.; Kwon,
Y.-U.; Jung, J.; Chang, J.; Hwang, Y. Catalytic Transfer Hydrogenation of Furfural to
Furfuryl Alcohol under Mild Conditions over Zr-MOFs: Exploring the Role of Metal
Node Coordination and Modification. ACS Catal. 10, 3720-3732 (2020).
[12] Gilkey, M.; Panagiotopoulou, P.; Mironenko, A.; Jenness, G.; Vlachos, D.; Xu, B.
Mechanistic Insights into Metal-Lewis Acid Mediated Catalytic Transfer
Hydrogenation of Furfural to 2-Methylfuran. ACS Catal. 5, 3988-3994 (2015).
[13] Berkessel, A.; Schubert, T. J.; Müller, T. N. Hydrogenation without a Transition-
s38
Metal Catalyst: On the Mechanism of the Base-Catalyzed Hydrogenation of Ketones.
J. Am. Chem. Soc. 124, 8693-8698 (2002).
[14] Ren, Y.; Yang, Y.; Chen, L.; Wang, L.; Shi, Y.; Yin, P.; Wang, W.; Shao, M.; Zhang,
X.; Wei, M. Synergetic Effect of Cu0−Cu+ Derived from Layered Double Hydroxides
toward Catalytic Transfer Hydrogenation Reaction. Appl. Catal. B. 314, 121515
(2022).
[15] Wang, H.; Shi, Y.; Wang, Z.; Song, Y.; Shen, M.; Guo, B.; Wu, L. Selective
Hydrogenation of Cinnamaldehyde to Hydrocinnamaldehyde over Au-Pd/Ultrathin
SnNb2O6 Nanosheets under Visible Light. J Catal. 396, 374-386 (2021).
[16] Wu, Q.; Zhang, C.; Arai, M.; Zhang, B.; Shi, R.; Peixuan, W.; Wang, Z.; Liu, Q.;
Liu, K.; Lin, W.; Cheng, H.; Zhao, F. Pt/TiH2 Catalyst for Ionic Hydrogenation via
Stored Hydrides in the Presence of Gaseous H2. ACS Catal. 9, 6425-6434 (2019).

s39

You might also like