Au/SiO2 based catalysts for propanol/propanal synthesis

from CO2, C2H4 and H2 in a dual-reactor system

Truong Duc Duc1, Pham Thi Mai Phuong2, Evgenii V. Kondratenko3’*,

Minh Thang Le1,*

1
School of Chemical Engineering, Hanoi University of Science and Technology, Dai Co
Viet Road, Hanoi, Vietnam
Advanced Institute of Science and Technology, Hanoi University of Science and
2

Technology, Dai Co Viet Road, Hanoi, Vietnam

3
Leibniz-Institut für Katalyse e.V. an der Universität Rostock (LIKAT)    
Albert-Einstein-Str. 29a, 18059 Rostock, Germany 
Corresponding authors: Evgenii.Kondratenko@catalysis.de, thang.leminh@hust.edu.vn
 ABSTRACT

CO2 hydrogenation to value-added products is a promising approach for controlling CO 2

emissions into the atmosphere. Agins this background, the group of Kondratenko has recently

reported about the production of propanol from C2H4, CO2 and H2 over supported Au-

containing catalysts fulfilling a dual role, i.e., the conversion of CO2 into CO and the

hydroformylation of C2H4 with CO. Although the selectivity to propanol with respect to CO 2

was close to 100%, the selectivity based on C 2H4 was only 15% due to high catalyst activity

for C2H4 hydrogenation to C2H6. In this work, we introduce and validate a dual-reactor

approach for improving the oxo-selectivity (propanol plus propanal). To this end, we

performed the RWGS reaction at high temperatures in the upstream-located reactor, while the

hydroformylation reaction was carried out at lower temperatures in the downstream-located

reactor without the need for expensive pre-separation of the product mixture from the first

reactor. Both reactors operated at same pressure. SiO 2-supported catalysts were used for both

reactions. The effects of temperature, total pressure, and the ratio of CO/H 2 adjusted through

temperature in the upstream-located reactor as well as Au loading content and Cs doping

content on the catalytic activity and oxo-selectivity were investigated. The highest oxo-

selectivity of 60% at ethylene conversion of 15% was achieved. The size of Au crystallites

was established to be an important selectivity-governing factor. This catalyst characteristic

depends on Au loading and Cs presence.

Keywords: hydroformylation, gold, SiO2, propanol, propanal, dual reactor

1 Introduction
Nowadays, fossil carbon-containing raw materials are still the major source of energy

and the main feedstock for a wide range of commodity chemicals. However, both energy

generation and chemicals production are typically accompanied by the formation of carbon

dioxide (CO2), which is the number one greenhouse gas. The scientific community generally

agrees that the continuously increasing concentration of this gas is the main reason for an

increase in the average temperature and thus contributes to global warming [1]. Therefore,

reducing CO2 release into the atmosphere is of enormous environmental interest. This can be

achieved by either capture/storage or utilization of this gas as a reactant for producing fuels

or/and useful chemicals in an environmentally friendly manner [2-3]. This is particularly valid

when CO2 is converted into long-time stable and usable products like polymers, dyes, or

resins, which are currently produced from ethylene and propylene. The latter building blocks

are currently generated from fossil carbon-containing feedstock through strongly endothermic

cracking reactions resulting in large CO2 emissions [4-7]. As CO2 conversion into value-

added alcohols and hydrocarbons requires H2, the production of the latter should also meet the

requirements for environmental compatibility. Water splitting powered through solar and/or

wind energy is a suitable option.

Propanal is an important chemical produced on the large scale over homogenous Co-

or Rh-containing catalysts through hydroformylation of C 2H4 using H2 and CO as additional

reactants. This aldehyde can be further hydrogenated to propanol, which is one of the basic

chemicals for the daily life [14]. Various heterogenous catalysts were also applied for gas-

phase hydroformylation of ethylene to propanal [8-11]. However, all hydroformylation

processes suffer from the usage of toxic CO gas at high pressure as well as decreased activity

with rising time on stream because of leaching of catalytically active species [12-13]. These

drawbacks can be overcome when using CO2 instead of CO and/or applying alternative

catalysts. In this regard, the group of Kondratenko developed supported Au-based catalysts
for the direct conversion of CO2 with H2 and C2H4 into propanol with near to 100% selectivity

to this alcohol with respect to CO2, while the selectivity with respect to C2H4 is below 15%

[15-19]. From a mechanistic viewpoint, this synthesis route is a multiple-step process

(equation 1-3) including the reverse water-gas shift reaction (RWGS) for in situ CO

generation [20], consecutive hydroformylation of C2H4 with CO and H2 to propanal [8] and

finally the hydrogenation of propanal to propanol [21]. The overall reaction is exothermic

with the enthalpy value being approximately 3 times higher than that for the methanol

synthesis from CO2.

RWGS reaction: CO2 + H2 ↔ CO + H2O (∆ r H 573 K =39 kJ·mol -1) (1)

Hydroformylation: CO + C2H4 + H2 → C2H5CHO (∆ r H 573 K =−130 kJ·mol-1) (2)

Hydrogenation: C2H5CHO + H2 → C3H7OH (∆ r H 573 K =−77 kJ·mol-1) (3)

Overall reaction: CO2 + C2H4 + 3H2→ C3H7OH + H2O (∆ rH573K = −167 kJ·mol−1) (4)

The main drawback of the up to now developed Au-containing catalysts for the

propanol formation from CO2 and C2H4 is their high activity towards undesired hydrogenation

of C2H4 to C2H6. It was also suggested that the RWGS and ethylene hydroformylation

reactions run independently on each other. Due to the thermodynamic constrains, these two

reactions require different operation temperatures to ensure high CO 2 conversion and high

propanal yield. The RWGS reaction runs above 573 K, while the hydroformylation reaction

runs efficiently below 473K [19]. Thus, a single-reactor concept with a dual-role catalyst is

not able to make a favor for both reactions, resulting in either low CO2 conversion or low

selectivity to propanol with respect to ethylene.

Against the above background the main objective of the present study was to elucidate

the potential of a dual-reactor approach for improving the yield of propanol and the

corresponding selectivity with respect to ethylene. To this end, we applied two fixed-bed

reactors connected in a series and operating at different temperatures but at same pressure.

The upstream-located reactor is used for the RWGS reaction to in situ generate CO, while the
desired hydroformylation reaction is carried out in the down-stream located reactor. From

mechanistic viewpoints, the focus was put on the effects of Au crystallite size, the presence of

Cs promoter and the ratio of CO/H2/CO2, which can be easily adjusted through varying

reaction temperature in the upstream-located reactor, on product selectivity in the

hydroformylation of ethylene.

2 Experimental
2.1 Catalyst preparation
Au/SiO2 was prepared through deposition–precipitation (DP) of gold hydroxide from

HAuCl4 (41.1 wt% Au, Chempur) on the support as follows. 2 g of SiO 2 powder and an

appropriate amount of HAuCl4 solution prepared by diluting 2g HAuCl4 in a 250 mL

volumetric flask were added under continuous stirring at room temperature to 100 mL water.

Water was further added to have 150 mL of the solution under stirring for 20 min.

Afterwards, an NH3 solution (25%, Roth) was slowly added until the pH value of 10 was

reached. After 10 min aging phase, the solid was filtered, washed, and finally dried in air at

80oC to yield Au/SiO2. Catalysts with Au loading of 0.5, 1, 2, or 4 wt% were prepared. Cs-

promoted Au/SiO2 catalysts were synthesized in two steps. First, Au/SiO 2 was prepared by the

DP method. The next step was incipient wetness impregnation of dried Au/SiO 2 with an

aqueous solution of CsNO3 (99.9%, Chempur). The loading of Cs was varied between 0.5 wt

% and 2 wt% Cs. The catalysts are denoted as xCs–yAu/SiO s, where “x” and “y” stand for the

particular Cs weight concentration and Au weight concentration, respectively (Table 1). All

catalysts were calcined in air at 300oC for 4 h and finally pressed and sieved to yield particles

with a sieve fraction of 250–450 μm.

2.2 Catalyst characterization

The weight concentration of Au and Cs in the calcined catalysts was determined by

inductively coupled plasma optical emission spectrometry (ICP-OES) using a Varian 715
emission spectrometer and atomic absorption spectroscopy (Perkin-Elmer Analyst 300),

respectively.

Nitrogen adsorption–desorption isotherms for all catalysts were collected at 77 K on a

BELSORP-mini II (BEL Japan, Inc.) setup. The specific surface area was calculated from the

adsorption isotherm applying the Brunauer-Emmett-Teller equation for the N 2 relative

pressure range of 0.05 < P/P0 < 0.30.

Powder X-ray diffraction (XRD) analysis was carried out using an X’Pert Pro

(Panalytical, Almelo) in the 2θ range of 5 − 80° and using a silicon standard. An average size

of Au crystallites was calculated from the reflection at 38.2° using the Scherrer equation.

TEM images were recorded on a JEM2100 microscope operated at 200 kV.

X-ray photoelectron spectroscopy (XPS) was applied for surface analysis of the

catalysts using a VG ESCALAB 220iXL instrument with monochromatic Al Kα radiation (E

= 1486.6 eV). The XPS spectra were described by Gaussian–Lorentzian curves after Shirley

background subtraction. The electron binding energy was referenced to the Au 4f7 signal of

Au0 cubic at 83.84 eV.

2.3 Catalytic tests

An in-house developed setup (at LIKAT) equipped with 2 continuous-flow fixed-bed

reactors operating in a series (a dual–reactor system) was applied for catalytic tests at 2 MPa

in the temperature range from 125oC to 250oC for the ethylene hydroformylation and from

350 -750oC for the RWGS reaction. 300 mg of 2AuSiO 2 catalyst (250–450 μm) was placed in

the upstream-located stainless-steel tube reactor (i.d. 4 mm) and heated up to 650 oC. 1000 mg

of an Au-containing catalyst (250–450 μm) was placed in the downstream-located stainless-

steel tube reactor (i.d. 16 mm). Initially, a flow of CO 2/H2/N2 = 1/1/1 was fed to the latter

reactor heated to 300oC for 2 hours to reduce Au 3+ to Au0. Hereafter, the reaction feed was

directed to the upstream-located reactor and the outlet gases of these reactor were fed to the

downstream-located reactor. In addition, a flow of C2H4 was fed to the latter reactor (not
passing through the upstream-located reactor) to yield an overall CO 2/H2/C2H4/N2 = 1/1/1/1

feed. The resulting contact time was 50 min·g·L-1. CO2 (4.5, Air Liquide), H2 (5.0, Air

Liquide), C2H4 (3.0, Linde), and N2 (5.0, Air Liquide) were used without any further

purification. Steady-state data were collected after at least 5 h of stabilization under each

condition.

The feed components and the reaction products were quantified by an on-line gas-

chromatograph (Agilent 7890A) equipped with a flame ionization detector (FID) and a

thermal conductivity detector (TCD). HP Plot/Q (for CO 2) and Molsieve 5A (for H2, O2, N2,

and CO) columns were connected to TCD, while AL/S (for CH 4, C2H4, C2H6, C3H6 and C3H8)

and FFAP (for oxygenates) columns were connected to FID.

The yield of propanal or propanol (Y (i, C 2H4)) based on C2H4 was calculated using

equation (5), under the consideration that one C2H4 is converted into propanal or propanol.

The conversion (X) of C2H4 was calculated according to equation (6) from the sum of these

yields and the yield of ethane calculated from equation (5). Equation (7) was used to calculate

the selectivity to propanal and propanol.

ni
Y(i, C2H4) = ×100 % (5)
nC H
2 4
, inlet

X(C2H4) = ∑ Y (¿ i , C2 H 4 ) ¿ (6)
i

Y (i, C 2 H 4 )
S(i, C2H4) = × 100 % (7)
X (C2 H 4 )

Where nC2H4,inlet stand for the mole flow of C2H4 at the reactor inlet and ni stand for the

mole flows of product i at the reactor outlet.

3 Results and discussion

3.1 Characterization of Au/SiO2 catalysts
The (ICP-OES) analysis revealed that Au loading slightly deviated from the theoretical

one (the number before Au in the catalyst formula) probably due to the loss of HAuCl 4 in the
filtrate. The experimentally determined values are given in Table 1. The Cesium content

almost corresponds to the theoretical loading since the deposition of Cs was performed by a

incipient wetness impregnation method without filtering.

The Brunauer–Emmett–Teller specific surface area (SBET) of bare support, fresh and

spent catalytic materials is listed in Table 1. The fresh catalysts possess surface area in the

range between 200 and 248 m2.g-1. There is a decrease in SBET after Au and/or Cs were

deposited. The decrease increases with an increase in the concentration of Au and Cs due to

blockage of support pores. The spent catalysts possess lower S BET values than their fresh

counterparts.

Table 1 Loading of Au and Cs, an average size of Au crystallites (dAu) as well as SBET values

of fresh and spent catalysts.

Catalysts Au loading Cs dAu SBET, SBET,

/ wt% a
loadin / nm c
fresh spent
g / m /g
2
/ m2/g
/ wt%b
SiO2 - - - 248 -
0.5Au/SiO2 - - 4 237 219
1Au/SiO2 0.97 - 6 233 210
2Au/SiO2 1.98 - 8 227 226
4Au/SiO2 3.88 - 9 220 205
0.5Cs1Au/SiO2 0.92 0.48 11 207 172
1Cs1Au/SiO2 0.94 0.99 10 201 63
2Cs1Au/SiO2 0.91 1.95 12 202 106
a
Au content was determined from ICP
b
Cs content was determined from AAS
c
Average crystallite size was calculated from the reflection at 38.2° using the Scherrer equation.

XRD analysis of monometallic and bimetallic catalysts after reduction in a hydrogen

flow at 250°C for 4h revealed the presence of cubic Au 0 metallic phase in (Figure 1). There is

no Cs2O crystal phase observed in Cs-Au/SiO2 which is probably due to the high dispersion of

this component. The size of the Au crystallites was calculated from the XRD reflection at
38.2° using the Scherrer equation after fitting with a pseudo-Voigt function. It increases from

4 to 8 nm with an increase in Au loading from 0.5 to 4 wt%. Depositing of Cs on the surface

of 1Au/SiO2 resulted in an increase in the size of Au crystallites, which is in an agreement

with previous studies [17, 18]. The increase in the size of Au crystallites in the present study

as well as a significant decrease in SBET between the fresh sample and spent catalysts could be

explained by water-induced (produced through the RWGS reaction in the upstream-located

reactor) transformation of Cs2O to Cs2SiO3 which resulted in a collapse of pore structure and

accordingly sintering of Au particles.

(a) (b)
Intensity / a.u.

Intensity / a.u.
2Cs1Au/SiO2
4Au/SiO2

2Au/SiO2 1Cs1Au/SiO2

0.5Cs1Au/SiO2
1Au/SiO2

0.5Au/SiO2 1Au/SiO2

0 20 40 60 80 0 20 40 60 80
2 Theta / ° 2 Theta / °

Figure 1 XRD patterns of reduced samples (by hydrogen at 250oC for 4h) (a) differently
loaded Au/SiO2 or (b) differently loaded Cs1Au/SiO2 samples.

TEM images of 1Au/SiO2 and 2Cs1Au/SiO2 are presented in Figure 2. Au particles with

a board size distribution in the range from 2 to 10 nm are seen on the surface of 1Au/SiO 2. An

average size is about 6 nm of diameter, which is in an agreement with the size of crystallites

obtained from XRD analysis (Table 1). In the sample 2Cs1Au/SiO2, Au particles are more

uniform with an average size of about 12 nm. In comparison with 1Au/SiO 2, their shape

changes from sphere to oval.

 (a) (b)

20 nm 20 nm

Figure 2 TEM images of (a) fresh 1Au/SiO2 (b) and 2Cs1Au/SiO2

X-ray photoelectron spectroscopy was applied to determine the oxidation state of Au in

fresh and spent catalysts. The obtained Au (Au4f peak) XP spectra are given in supporting

information S1. For all fresh catalysts, the signals with maxima at 84eV and 88eV are belong

to the Au3+ state. Contrarily, only Au0 state characterized by signals at 83eV and 87eV was

identified in all spent catalysts, which had been in situ reduced in H 2 before the catalytic

reaction.

3.2 Catalytic performance according to single and dual-reactor approaches

Using a single-bed reactor, ethane was identified to be the main product in the

hydroformylation of ethylene with CO2 over 1Au/SiO2 at 175 and 200°C (Figure 3(a)).

Propanal/propanol are formed in trace amounts only. The conversion of ethylene is near to

complete. The preferential ethylene hydrogenation should be related to the low catalyst

activity in the RWGS reaction to generate CO requiring for the desired hydroformylation

reaction. From a thermodynamic viewpoint, temperatures higher than 300oC are necessary for

the RWGS reaction, while the hydroformylation reaction should run below 250°C.
 (a)

X (C2H4), S (C2H6) or S (oxo) / %

CO2 + H2
100

80 T=175ƒC T=200ƒC

60

40

20

0
0 2 4 6 8
Products
Time on stream / h
(b)

X (C2H4), S (C2H6) or S (oxo) / %

CO2 + H2 Products
100 T=175ƒC T=200ƒC

80

60

40

20

0
H2, H2O 0 2 4 6 8
C2H4
CO, CO2 Time on stream / h

Figure 3 Ethylene conversion (X(C2H4)) and the selectivity to propanal and propanol
(S(oxo)) in the hydroformylation of ethylene over 1Au/SiO 2 at 175 or 200°C and
pressure of 20 bar using (a) a single reactor or (b) a dual-reactor approach, where
two reactors are connected in a series. Contact time in the downstream-located
reactor used for the ethylene hydroformylation: 50 g·min·L -1 , catalyst amount: 2
g, temperature of the upstream-located reactor used for the RWGS reaction:
650oC, total pressure: 20 bar, nominal feed composition : CO 2/H2/C2H4/N2 =
1/1/1/1.

Product selectivity and the conversion of ethylene change strongly when performing the

hydroformylation of ethylene according to a dual-reactor approach (Figure 3(b)). The

conversion is only 13 and 30% at 175 and 200°C, respectively, in comparison with 100% in

the single-bed reactor. The suppressed ethylene conversion can be related to the negative

effect of CO [15]. It is also worth mentioning that the oxo-selectivity (propanal plus propanol)

turns from almost 0% (single reactor) to 60 or 45% (dual-reactor approach) at 175 or 200 oC.

Oppositely the selectivity to ethane decreases from 100% to 40 or 55%. The main oxo-

product is propanal (Figure S2). Such high oxo-selectivity has never been achieved in

previous studies dealing with ethylene hydroformylation with CO over Au/TiO 2 and Au/SiO2

catalyst [2, 9, 10]. Thus, these results clearly demonstrate the potential of our dual-bed reactor
approach for the production of propanal/propanol using a feed containing ethylene, carbon

dioxide and hydrogen.

3.3 Effects of Au and Cs loading

To check if and how the size of Au nanoparticles affects selective and unselective

pathways in the course of ethylene hydroformylation over Au/SiO 2 catalysts, we varied Au

loading between 0.5 and 4 wt.% (Table 1). The catalysts were tested at 175 and 200°C

according to the dual-reactor approach. The temperature of the upstream-located reactor used

for the RWGS reaction was 650°C. The steady-state values of ethylene conversion and oxo-

selectivity are shown in Figure 4 as a function of Au loading. The corresponding values for

the selectivity to propanal and propanol are given in Figure S3. Importantly, the catalysts

were tested at same contact time. Thus, the conversion of ethylene is a direct measure of their

activity. Both the conversion and the selectivity pass over a maximum but at different Au

contents (Figure 4). The highest activity was achieved over 2Au/SiO 2. However, 1Au/SiO2

reveals the highest oxo-selectivity. As ethane and propanal are formed through parallel

pathways, the different selectivity values are not due to the different degrees of ethylene

conversion but should be related to the effect of the size of Au NP on the kinetics of the

hydrogenation and hydroformylation reactions. Au NP of about 6 nm seem to be required for

the latter reaction.

80 80
(a) (b)
T=200ƒC
60 60 T=175ƒC
X(C2H4) / %

S(oxo) / %

T=200ƒC
40 40
T=175ƒC

20 20

0 0
0 1 2 3 4 0 1 2 3 4
Au loading / wt% Au loading / wt%
Figure 4 (a) The conversion of ethylene and (b) the selectivity of oxo products obtained
over differently loaded Au/SiO2 catalysts tested according to a dual-reactor
approach, where two reactors are connected in a series. Contact time in the
downstream-located reactor used for the ethylene hydroformylation: 50 g·min·L-1 ,
 temperature of the upstream-located reactor used for the RWGS reaction: 650 oC,
total pressure: 20 bar, nominal feed composition: CO2/H2/C2H4/N2 = 1/1/1/1.

1Au/SiO2 and 2Au/SiO2 were selected for analyzing the effect of reaction temperature

on the ethylene hydroformylation in a broader range, i.e., between 125 and 250°C. As

expected, the conversion of ethylene increases with rising reaction temperature. 2Au/SiO 2

shows higher activity than 1Au/SiO2 in the whole temperature range (Figure 5). In contrast to

the conversion, the oxo-selectivity decreases with an increase in temperature. The ratio of

propanal/propanol, however, increases (Figure S4). Au loading also has a positive effect on

this ratio. The highest oxo-selectivity of about 70% was achieved over 1Au/SiO2 at 125°C

(Figure 5). In general, this catalyst outperforms 2Au/SiO 2 in this regard. For both catalysts,

the negative effect of temperature on the oxo-selectivity is less pronounced between 125 and

175°C than at higher temperatures. As these catalytic tests were carried out under conditions

far from equilibrium, the effect of temperature is due to the different activation energies of the

hydrogenation and hydroformylation reactions. The latter reaction requires less energy to

proceed.
X(C2H4), S(oxo) or Y(oxo) / %

100
(a) 1Au/SiO2 (b) 2Au/SiO2
80

60

40

20

0
125 150 175 200 225 250 125 150 175 200 225 250
Temperature / °C Temperature / °C
Figure 5 The effect of temperature in the downstream-located reactor on ethylene
conversion (X(C2H4)), oxo-selectivity (S(oxo)) and oxo-yield (Y(oxo) over
1AuSiO2 and 2AuSiO2. Contact time in the downstream-located reactor: 50
g·min·L-1, temperature of the upstream-located reactor used for the RWGS
reaction: 650°C, total pressure: 20 bar, nominal feed composition:
CO2/H2/C2H4/N2 = 1/1/1/1.

Since the 1Au/SiO2 catalyst shows the highest oxo-selectivity, we decided to investigate

the effect of Cs promoter on performance of this material. The concentration of the promoter
was varied between 0.5 and 2 wt%. Hydroformylation catalytic tests were carried out at 175

and 200°C, while the temperature for the RWGS reaction was fixed at 650°C. The promoter

has a strong negative effect on the conversion, which decreases from 13 to 2.7% at 175°C or

from 30 to 3% at 200°C with an increase in Cs loading from 0 to 2 wt% (Figure S5). The

negative effect of Cs can be explained as follows. First, the promoter causes an increase in the

size of Au NP, which seems to be detrimental for the activation of H 2 required both for the

hydrogenation and hydroformylation reactions. Second, as shown in our previous study

dealing with Cs-Au/TiO2 catalysts [17], the promoter partially covers the surface of Au NP,

thus hindering ethylene adsorption.

3.4 Effects of reaction pressure and CO/H2 ratio

To check the effect of pressure on oxo-production in our dual-reactor approach,

catalytic tests were carried at 175°C between 1 and 20 bar using 1AuSiO 2. Figure 6 shows

that the conversion of ethylene and the oxo-selectivity increase with rising total pressure. The

highest selectivity of about 60% was achieved at 13% ethylene conversion and 175°C. As H 2

is required both for the hydrogenation of ethylene to ethane and for the formation of propanal

from ethylene, the positive effect of H2 on the oxo-selectivity cannot be explained by

pressure-induced improvement of activation of this reactant. On this basis, we put forward

that CO activation should be enhanced with an increase in its partial pressure. This

assumption is supported by the below results obtained upon varying the ratio of CO/H2.
Figure 6 Effect of total pressure on the conversion of C 2H4 and the selectivity to oxo
products over 1AuSiO2 at 175°C. Contact time in the downstream-located reactor:
50 g·min·L-1 , temperature of the upstream-located reactor used for the RWGS
reaction: 650oC, total pressure: 20 bar, nominal feed composition:
CO2/H2/C2H4/N2 = 1/1/1/1.

The CO/H2 ratio was varied by changing the temperature (from 350 – 750 oC) in the

upstream-located reactor used for the RWGS reaction, while the temperature of the

downstream-located reactor used for the hydroformylation reaction was 175 oC or 200oC.

Figure 7 shows that both the oxo-selectivity and the oxo-yield increase with an increase in this

ratio. For example, the oxo-selectivity over 1Au/SiO 2 at 170oC increases from 24 to 60% with

an increase in the CO/H2 ratio 0.1 to 0.6. A further increase in the ratio to 0.78 did not

improve the selectivity. Thus, CO activation (CO partial pressure) is an important factor

affecting the formation of the desired products. When reaction temperature increased to

200°C, the oxo-selectivity decreased, while the oxo-yield increased due to higher ethylene

conversion. Nevertheless, an optimal CO/H2 ratio is about 0.6 and 0.7. This is understandable

since these values are close with the value for classical ethylene hydroformylation (equation

1).
 a) b)

Figure 7 Effect of CO/H2 ratio achieved through varying reaction temperature of the
upstream-located reactor on the oxo-selectivity and oxo-yield over (a) 1AuSiO 2
and (b) 2Au/SiO2 at 175 and 200°C. Contact time in the downstream-located
reactor: 50 g·min·L-1 , total pressure: 20 bar, nominal feed composition:
CO2/H2/C2H4/N2 = 1/1/1/1.

In the course of ethylene hydroformylation, propanol is primarily formed from this

olefine and can be further hydrogenated to propanal. Thus, we now analyze how the ratio of

CO/H2 and Au loading affect the ratio of propanol/propanal. Regardless of Au content, the

fraction of propanol decreases with an increase in the CO/H 2 ratio (Figure S6). It is higher at

200°C than 175°C and over 2Au/SiO2 than over 1Au/SiO2. As H2 is required for the

hydrogenation of propanal to propanol, the negative effect of rising CO/H 2 ratio on the

fraction of propanol is simply related to low partial pressure of H 2. The size of Au NP seems

to be an additional parameter influencing the formation of propanol. The fraction of this

oxygenate is significantly higher for 2Au/SiO2 than for 1Au/SiO2 (Figure S6). These catalysts

differ in the size of Au NP with 2Au/SiO2 possessing larger particles.

4 Conclusions
The present study has demonstrated that performing heterogeneous conversion of C 2H4

with CO2 and H2 to propanal/propanol over SiO2-supported Au-containing catalysts according

to a dual reactor approach is an attractive option for improving the selectivity to the desired

products. Owing to spatial separation of RWGS and C 2H4 hydroformylation reactions, the

undesired hydrogenation of ethane to ethylene can be hindered in favor of oxo-products

formation through controlling CO partial pressure for the hydroformylation reactor. The
selectivity to oxo-products decreases with an increase in reaction temperature due to lower

activation energy of propanal formation in comparison with that of ethane formation. The

oxo-selectivity of about 60% was achieved at about 15% ethylene conversion under optimized

reaction conditions. No obvious catalyst deactivation was observed.

Concerning catalyst design, both the overall activity and the oxo-selectivity depend on

the size of Au nanoparticles. The highest performance was achieved when an average size is

about 6nm, which seems to be suitable for the hydroformylation of ethylene. Smaller of larder

nanoparticles are not active for hydroformylation but promote the undesired hydrogenation of

C2H4 to C2H6.

Acknowledgments

This research is funded by Vietnam National Foundation for Science and Technology

Development (NAFOSTED) under grant number 104.05-2017.333

Truong Duc Duc gratefully thanks to RoHan Project funded by the German Academic

Exchange Service (DAAD, No. 57315854) and the Federal Ministry for Economic

Cooperation and Development (BMZ) inside the framework "SDG Bilateral Graduate school

programme” for a part time PhD scholarship to LIKAT.

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