Andrey A. Rybakov* a
, Ilya, A. Bryukhanov b
, Alexander V. Larin a
,
Georgy M. Zhidomirov a, c a
Department of Chemistry, Moscow State University, Leninskie Gory, Moscow, GSP-2, Russia
119992; b Department of Mechanics and Mathematics, Moscow State University, Leninskie
Gory, Moscow, GSP-2, 119992 Russia; c
Boreskov Institute of Catalysis, SB RAS, Novosibirsk,
630090, Russia
Ph. 7-495-939-3952, Fax 7-495-932-8846
*)
rybakovy@gmail.com

S1. Water influence on Cu-carbonate formation
Regarding the easiness of CH
4
oxidation over CuO
X
Cu moieties [S1-S4], one can propose that CO oxidation to CO
2
should not be a limiting stage. Then the Cu-carbonate formation via the reactions between CO
2
and CuO
X
Cu moieties can be tested similarly to the route from EA oxide MeO
X
Me clusters [S5-S6], X = 1 - 2. The Part 3.2 justifies the application of the DFT tools relative to our cluster models containing CuO
X
Cu moieties, X = 1 - 2, which can react to produce the carbonates. We can now check: 1) the activation energy of carbonate formation due to the reaction between CO
2
and CuOCu species and 2) how the reaction of carbonate formation will depend on the presence of water. A reaction cycle will have additional attraction if the reaction will not require a high temperature treatment for full dehydration.
The reaction of CO
2
and CuOCu-8R(2Al) without water presents a first problem at the step of the reagents optimization. We have optimized a metastable structure (-3489.990800 a.u. in Table S1, Fig. S1a) which is less stable than the separated reagents (at infinity) (-3489.998780 a.u. in Table S1) and respective transition state (TS) (Fig. S1b). The Cu-O distance for the closest O atom of CO
2
is 2.498 Å, the latter is tilt relative to one of the cations with a minor deformation (

O-C-O = 177.6°, |C-O| = 1.163 and 1.177 Å). While using the metastable structure as reagents for the search of the TS geometry with QST3 method [S7], we have obtained the TS geometry (Fig. S1b) with required frequency of 268 i cm
-1
which is more stable than the structure (Fig. S1a) but less stable than separated reagents (Table 8). If one use the energy of the separated reagents as the estimation of the reagent energy, then the activation barrier for the CuCO
3
Cu formation can be conventionally evaluated E a
< 2.36 kcal/mol without water. This small barrier shows quick trapping of CO
2
by CuOCu at room temperature.
This activation energy rises only up to 5.18 kcal/mol if one water molecule is coordinated to the Cu cation of CuOCu-8R(2Al) which is not linked to CO
2
(Fig. S1f). Such structure with non-dissociated water (Fig. S1f) remains more stable (as much as by 18.09 kcal/mol) than

possible hydrocarbonate (HO)CuНCO
3
Cu(8R) (Fig. S1g). We did not succeed to find the TS geometry for its transformation into (H
2
O)CuCO
3
Cu(8R) using cluster approach. Once looking for a stable configuration for dissociated water with proton at the O atom of the 8R ring we observed the easy recombination of water and thus obtained more symmetric and more stable carbonate geometry together with water (Fig. S1j) than the asymmetric one (Fig. S1f) achieved via the reaction of CuOCu with CO
2
(Fig. S1c, f) whose configuration does not depends on the presence of adsorbed water. In the terms of

(Eq. 1) asymmetry parameter, this more symmetric carbonate possesses

of 0.083 Å (Fig. S1j) instead of 0.243 Å for asymmetric one. In order to evaluate respective band splitting (BS) one could address to Fig. 1 of ref. [S8] (or Fig. 4 from ref. [S9]) where the fitted linear approximation BS(

) at the B3LYP/6-31G* level is depicted by dotted line. Then

= 0.083 Å corresponds to the BS value around of 220-230 cm -1 from the
Figure 1 of ref. [S8] that is in good agreement with experimental BS values of 226 cm
-1
[S10] or
221 cm
-1
[S11]. It signifies that the carbonate (Fig. S1j) suits very well to the spectroscopic data about the observed species which exists along the DMC formation reaction in CuY [S10-S11]
1
.
Moreover, carbonate is stable in a reaction with water.
We have observed a moderate reactivity of the CuOCu-8R(2Al) cluster relative to the water. Its heat of adsorption takes 21.1 kcal/mol without the zero point energy (ZPE) variation.
This heat value is in the usual range for the heats of water adsorption at the zeolites with transition metal cations [S12]. The minor shift of the ZPE can be evaluated from the ZPE variation upon adsorption in similar systems, i.e., less than 0.4 and 0.6 kcal/mol at Mg 2+ и Ca 2+ forms, respectively [S13-S13]. The non-dissociated state is favored for water in the Cu8R(2Al) cluster with a recombination barrier of 2.3 kcal/mol and imaginary frequency of 1228 i cm
-1
(Fig.
S1k). In this respect the Cu
+2
resembles the EA cations [S13-S13].
1 However, this more symmetric form slightly varies upon the loss of water (not shown) achieving

= 0.079 Å being less stable than the asymmetric one (-3490.027523 a.u. in Table 8) by 1.2 kcal/mol.

References
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Table S1. The energies (

U, kcal/mol) of the formation steps (a.u.) of copper carbonate in the cluster Z = 8R(2Al) with and without water and activation energy (E a
, kcal/mol). The barriers for
TS are shown in Figure S1. Activation energy or heat of the reactions (given in Fig. S1) are shown in brackets for TS or products, respectively.
System
<Cu
2
O-Z + CO
2
>
Isolated Cu
2
O-Z and CO
2
TS (E a
= <2.4> b)
)
Cu
2
CO
3
– Z (

U = -24.3)
(H
2
O)Cu
2
O-Z + CO
2 а)
-U, a.u.
<3489.990800>
3489.998780
3489.995014
3490.029590
3566.439243
TS (E a
= 5.2) 3566.430990
(H
2
O)Cu
2
CO
3
– Z (

U = -19.4) 3566.470210
(HO)CuНCO
3
Cu-Z
(HO)Cu-O(H)-Cu-Z + CO
TS (E a
= 15.7) a)
(H
2
O)Cu
2
CO
3
– Z
Cu
2
CO
3
– Z
(HO)Cu – HZ
2
3566.441374
3566.443558
3566.418523
3566.475126
3490.027523
3106.462957
Figure
S1a
-
S1b
S1c
S1d
S1e
S1f
S1g
S1h
S1i
S1j
-
-
TS (E a
= 2.3)
(H
2
O)Cu – Z
3106.459254
3106.476524
S1k
-
H
2
O
CO
2
76.407024
188.577570
-
-
Cu
2
O– Z 3301.421210 - а)
the reagents are (HO)Cu-O(H)-Cu-Z + CO
2
(Fig. S1h), while the product is Cu
2
CO
3
– Z + H
2
O
(see the text); b)
relative to the energy of isolated Cu
2
O-Z + CO
2 species

Figure caption
Figure S1. Local geometries of (a, d, h) reagents, (b, e, i, k) transition states, (c, f, g, j) products of the reactions between the Cu
2
8R(2Al) cluster and CO
2
or/and H
2
O optimized at the B3LYP/6-
31G* level. Only transition state (k) for H
2
O dissociation is shown. The arrows connect three steps of three reactions (reagent

transition state

product, two of them possess a common product (f)). More data about the structures are collected in Table 8. The atomic colors are given in blue, red, yellow, magenta, and grey for Cu, O, Si, Al, and H, respectively.

g) j) a) d)
Figure S1 b)
 E a
< 2.4
c) e)

E a
= 5.2
f) h) i)

E a
= 15.7
k)
 E a
= 2.3