A Bimetallic Pure Inorganic Framework for Highly Eꢀcient and Selective Photocatalytic…
by using N as adsorbent on an ASAP 2460 Micromeritics
2.4.2 Thermal Catalysis Oxidation of Cyclohexene at Higher
2
instrument at 77 K.
Pressure
The oxidation oꢀ cyclohexene at higher pressure was car-
ried out in a stainless steel autoclave (25 mL) with the cata-
lyst (0.01 mmol) and solvent (3 mL) were added, then the
substrate cyclohexene (10 mmol, 15 mg) was added to the
mixture solution. Subsequently, the autoclave was sealed
2
.2 Preparation of CoMo
CoMo was prepared under hydrothermal conditions by
the selꢀ-assembly approach: Co(NO ) ·6H O (270 mg,
3
2
2
1
.13 mmol) and Na MoO ·2H O (340 mg, 1.39 mmol) were
and preꢃlled with 0.5 MPa oꢀ O , placed in an oil bath with
2
4
2
2
dissolved in 6.0 mL mixed solution oꢀ water and acetonitrile
desired temperature and reaction time. At the end oꢀ reac-
tion, aꢀter the autoclave cooled to room temperature the
excess gases were vented. The remaining mixture was ꢃl-
tered and evaporated under reduced pressure to obtain the
with the ratio oꢀ 4:2, the resultant mixture was stirred over
−
1
1
0 h. Then using a dilute HCl solution (0.5 mol L ) and
adjusted the above mixture to 3 oꢀ pH value, then sealed
in a 25 mL Teꢂon-lined autoclave, and heated at 150 °C
1
product. The conversion and selectivity were obtained by H
ꢀor 3 days. Aꢀter the autoclave cooled to room temperature,
NMR analysis oꢀ the ꢃnal solution aꢀter reaction.
purple single crystals were ꢃltrated and washed with water,
then dried naturally at room temperature. The pure crystals
were obtained with a high yield oꢀ 73%, based Mo element.
ICP (%). Anal. Calcd. For CoMoNa HO : Na, 4.65; Co,
3 Results and Discussion
0
.5
5
2
3.82; Mo, 38.78. Found: Na, 4.63; Co, 23.83; Mo, 38.80.
3.1 Crystal Structure of Complex CoMo
The single crystal diꢁraction analysis reveals that CoMo
crystallizes in the monoclinic space group C2/m, an asym-
metric unit oꢀ CoMo consists oꢀ a sodium atom, a tetrahe-
2
.3 Photocatalytic Oxidation of Cyclohexene
The photocatalytic reaction was carried out in a Pyrex ves-
sel, in which the substrate cyclohexene (10 mmol), catalyst
dral {MoO } group, and two crystallographically uniꢀorm
4
cobalt ions (Fig. S1). Among them, each cobalt ion adopts
octahedral coordination geometry by six oxygen atoms, and
cobalt ions ꢀorm a one-dimensional chain through sharing
two bridging oxygen atoms in their equatorial planes (Fig.
S2). The two exposed bridge oxygen atoms are protonated as
calculated by valence-bond method. The molybdenum ions
as linkers constitute two-dimensional plane with cobalt ions
and bridging oxygen atoms, halꢀ oꢀ them link with equato-
rial oxygen atoms oꢀ cobalt octahedron and the others stand
on the polar sites oꢀ cobalt octahedron by the oxygen oꢀ
(
0.01 mmol, 15 mg) and solvent (3 mL) were added. Then
it was ꢃlled with 0.1 MPa O with a balloon at room tem-
2
perature. Aꢀterwards, the Pyrex vessel was irradiated under
4
20–500 nm blue or white light ꢀor luminous power oꢀ 10 W.
Aꢀter reaction to desired time, the ꢃnal mixture was ꢃltered
and evaporated under reduced pressure to obtain the product.
1
The conversion and selectivity were obtained by H NMR
analysis oꢀ the ꢃnal solution aꢀter reaction.
{
MoO } groups (Fig. 1b). The layers oꢀ two-dimensional
4
2
+
6+
2.4 Thermal Catalysis Oxidation of Cyclohexene
planes constituted by Co and Mo ions are linked by
sodium ions to ꢀorm a three-dimensional ꢀramework with
two kinds oꢀ pores, named A and B (Fig. 1c, d). The pore
A oꢀ has an approximate dimension oꢀ ca. 3.956 × 4.686
Å, and an approximate dimension oꢀ 3.955× 4.073 Å ꢀor
pore B (Fig. S3). Both pores ꢀormed catalysis channels are
2.4.1 Thermal Catalysis Oxidation of Cyclohexene
at Normal Pressure
The oxidation oꢀ cyclohexene at normal pressure was car-
ried out in a round bottom ꢂask (25 mL) with the catalyst
2
+
6+
adequately capacious allowed Co and Mo sites ꢀavoring
contact with cyclohexene and oxygen substrates. Moreover,
the bare cobalt sites have the ability to ꢃx and activate oxy-
gen and ꢀorm peroxo or superoxo species, which ꢀurther pro-
duce oxygen radicals to make the oxidation oꢀ labile allylic
hydrogen atoms in cyclohexene more smoothly. The PXRD
oꢀ CoMo displays good correspondence between the simu-
lated and experimental patterns, which suggests the high
purity oꢀ the samples (Fig. S4). TGA revealed the CoMo
ꢀramework is stable up to ~ 350 °C, which exhibits this
catalyst has high thermal stability. Above characteristics oꢀ
(
0.01 mmol) and solvent (3 mL) were added, then the sub-
strate cyclohexene (10 mmol, 15 mg) was added to the
mixture solution. Subsequently, the round bottom ꢂask was
sealed with a balloon which was preꢃlled with 1 atm oꢀ O .
2
Then, the round bottom ꢂask was placed in an oil bath with
desired temperature and reaction time. At the end oꢀ the
reaction, the ꢃnal mixture was ꢃltered and evaporated under
reduced pressure to obtain the product. The conversion and
1
selectivity were obtained by H NMR analysis oꢀ the ꢃnal
solution aꢀter reaction.
1
3