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Highly Dispersed Metal Doping to ZnZr Oxide Catalyst for CO2 Hydrogena-
tion to Methanol: Insight into Hydrogen Spillover

Di Xu, Xinlin Hong, Guoliang Liu

PII: S0021-9517(20)30493-0
DOI: [Link]
Reference: YJCAT 13999

To appear in: Journal of Catalysis

Received Date: 19 October 2020

Revised Date: 28 November 2020
Accepted Date: 30 November 2020

Please cite this article as: D. Xu, X. Hong, G. Liu, Highly Dispersed Metal Doping to ZnZr Oxide Catalyst for
CO2 Hydrogenation to Methanol: Insight into Hydrogen Spillover, Journal of Catalysis (2020), doi: https://
[Link]/10.1016/[Link].2020.11.039

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Highly Dispersed Metal Doping to ZnZr Oxide

Catalyst for CO2 Hydrogenation to Methanol: Insight

into Hydrogen Spillover

Di Xu1, Xinlin Hong1*, Guoliang Liu1*

1 College of Chemistry and Molecular Sciences, Wuhan University, Wuhan 430072, China

*Corresponding authors.

Email addresses: hongxl@[Link] (X. Hong); liugl@[Link] (G. Liu)

KEYWORDS

Cu doping, CO2 hydrogenation, methanol synthesis, solid solution catalyst, hydrogen spillover

ABSTRACT

Metallic oxide based catalysts have received much attention in CO2 hydrogenation to methanol

because of their high methanol selectivity and long-term stability. But the relatively weak

1
hydrogenation ability leads to low methanol activity. Here, we introduce a small amount of Cu

(molar fraction<2%) into ZnZrOx to form ternary metal oxide solid solution catalysts (x% CuZnZr)

to promote methanol production. The optimized 0.5% CuZnZr catalyst performs CO2 conversion

of 9.5% and methanol yield of 7.2%, both of which are about 4 times that of ZnZr catalyst at

comparable methanol selectivity (76% versus 80%) at 290 ºC. Chemisorption and in situ diffuse

reflectance Fourier transform infrared spectroscopy (DRIFTS) analyses reveal that the enhanced

activity is attributed to the improved hydrogenation capacity and accelerated transformation of

HCOO* to CH3O* caused by hydrogen spillover from well dispersed Cu. This can also be applied

to trace amount of Pd or Pt doping to ZnZrOx.

Introduction

The consumption of fossil fuels accompanied by massive release of CO2 has led to the severe

seawater acidification and climate change.1,2 Converting CO2 to methanol using hydrogen from

renewable energy sources is one of the most potential processes to achieve carbon-neutral cycle

since methanol can act as a C1 platform intermediate for valuable chemicals (e.g., olefins,

aromatics) and fuels (e.g., gasoline), or be directly used as clean fuel.3-5 In CO2 hydrogenation, the

methanol synthesis would compete with the reverse water-gas shift (RWGS) reaction, especially

at high CO2 conversion. In this content, the development of highly selective and active methanol

synthesis catalysts remains a persistent challenge.

Traditional Cu-ZnO-Al2O3 catalyst is very efficient for methanol production from CO2

hydrogenation, but it still suffers from low methanol selectivity caused by the considerable activity

towards RWGS and poor stability.6-8 Lately, ZrO2-containing Cu-based catalysts are widely

2
studied because of the versatile properties and weak hydrophilic character of ZrO2.9-14 As another

important catalyst system developed in recent years, metallic oxide catalysts (e.g., Cr2O3, ZnCrOx,

In2O3, In2O3-ZrO2, and MaZrOx [Ma = Zn, Cd, Ga] solid solution) have attracted intensive attention

because of their high methanol selectivity and excellent stability towards sintering and sulfur

toleration,15-21 or easy coupling with zeolites to achieve direct CO2 conversion to C2+ products.22-
29 Among these catalysts, the advanced In2O3-ZrO2 metallic oxide and ZnZrOx solid solution

catalysts show superior methanol selectivity (> 80% at a reasonably high CO2 conversion

(>5%)),17,18 but they still requires high operating reaction temperature (300-350 ºC) due to the

weak hydrogenation ability. Therefore, our goal is to improve the low-temperature activity of

metallic oxide catalysts but still maintain their superior methanol selectivity and stability.

It is known that ZnO can dissociate molecular hydrogen heterolytically to yield Zn2+-H- bond

which can take part in hydrogenation reaction at high temperature.30-32 The relatively poor

hydrogenation activity is crucial to olefin or aromatic synthesis from CO/CO2 hydrogenation over

coupled metallic oxide-zeolite catalysts.23,29 Wang et al. reported that Zn or Cd is responsible for

hydrogen activation in ZnZrOx or CdZrOx solid solution catalysts, which would affect CO2

conversion.18,19 It is supposed that the poor activity of ZnZrOx solid solution catalysts at low

temperature is probably due to the weak hydrogenation capability. Frei et al reported that the

apparent reaction orders of H2 and CO2 in methanol synthesis over In2O3/m-ZrO2 are 0.3 and 0,

while those over In2O3/t-ZrO2 are 0.5 and -0.1.33 This implies that the H2 activation has a bigger

effect on methanol synthesis than CO2 activation over oxide catalysts. Metals can readily

dissociate dihydrogen, which are beneficial to hydrogenation reaction and methanol synthesis.34,35

Cu are supposed to dissociate H2 over Cu-ZrO2 catalysts for CO2 hydrogenation to methanol.13.36,37

3
Based on the above analyses, the introduction of transition metal may improve the catalytic activity

of ZnZrOx catalysts.

In this work, we prepared a series of CuZnZrOx solid solution catalysts with small amount of

Cu content (0.2%, 0.5%, 1% and 2%) to study the role of Cu doping in methanol synthesis. Cu

greatly increases the CO2 conversion but decreases the methanol selectivity to some extent. Under

a kinetic control condition (290 ºC, 4.5 MPa), the optimized 0.5% CuZnZr catalyst exhibits the

CO2 conversion of 9.5% and methanol yield (7.2%) which are more than 4 times that of un-

promoted ZnZr catalyst while the selectivity does not change much (76% versus 80%). It is

demonstrated that Cu doping improves methanol formation rate kinetically via accelerating the

hydrogenation rate of key intermediates by using H2 temperature-programmed reduction (TPR)

and in situ DRIFTS characterizations. The high dispersion of Cu in ZnZrOx solid solution and the

improved hydrogenation capability are crucial to selective and active methanol synthesis from CO2

hydrogenation.

Experimental Section

Catalyst preparation. The series of CuZnZr catalysts were prepared by a coprecipitation method.

Typically, 5.8 g Zr(NO3)4·5H2O (13.5 mmol, ≥ 99% pure, Sinopharm Chemical Reagent), 0.6 g

Zn(NO3)2·6H2O (2 mmol, ≥ 99% pure, Sinopharm Chemical Reagent) and a proper amount of

Cu(NO3)2·3H2O (≥ 99% pure, Sinopharm Chemical Reagent) were dissolved in deionized water

(0.155 M) in a flask. The molar percent of Cu2+ varied from 0 to 0.2%, 0.5%, 1%, and 2%.

(NH4)2CO3 aqueous solution (0.32 M) was then added to above solution with a drop rate of 3 mL

min-1 under vigorous magnetic stirring at 70 ºC until the pH of solution reached 9.0. The

4
suspension was kept stirring for 2 h at 70 ºC and then cooled down to room temperature naturally.

The resulting precipitate was collected by centrifugation and washed with deionized water for 3

times, followed by drying at 110 ºC for 4 h and calcination at 500 ºC for 3 h. The product is denoted

as x% CuZnZr.

0.02% Pd (or Pt) doped ZnZrOx catalysts were prepared by an impregnation method. A proper

amount of Pd(NO3)2·2H2O (≥ 98% pure, Aladdin) or H2PtCl6·6H2O (≥ 98% pure, Aladdin) was

dissolved in 5 mL deionized water. And 1 g ZnZr powder was added to above solution under

magnetic stirring at room temperature for 6 h. The suspension was dried at 110 ºC for 12 h and

calcined at 500 ºC for 3 h. The product is denoted as 0.02% PdZnZr or 0.02% PtZnZr.

Catalyst characterization. Transmission Electron Microscopy (TEM) images were acquired on

a JEM-2100 (JEOL) at 200 kV. Elemental mapping was carried out on a JEM-F200 (JEOL).

Before the characterization, the catalyst was dispersed in ethanol and then deposited on a carbon

film. N2 sorption isotherms were collected at 77 K on an ASAP 2020 (Micromeritics) to calculate

the Brunauer-Emmett-Teller (BET) surface area and pore volume. Powder X-ray diffraction

(PXRD) was recorded on a Bruker D8 Advances with a Cu Kα radiation. The catalysts were

scanned from 20° to 80° with a step angle of 0.02°. The mean grain size of each sample was

calculated with the Scherrer formula. X-ray photoelectron spectroscopy (XPS) was performed on

a Thermo Fisher Scientific ESCALAB 250Xi X-ray Photoelectron Spectrometer with Al K

radiation (15 kV, 10 mA, hν = 1486.6 eV). The sample was reduced by 10% H2/Ar at 400 ºC for

1 h before test. All data were corrected by the binding energy of C1s (284.8 eV) adventitious

carbon.

5
 H2-TPR experiments were carried out on a Micromeritics Autochem 2920 to study the reducing

features of our catalysts. The experimental procedure was described as follows. 100 mg sample

was loaded on the layer of quartz wool in a U-shaped quartz tube and was heated to 250 ºC with a

heating rate of 10 ºC min-1 in Ar flow (30 mL min-1) for half hour to remove the adsorbed dirt.

After cooling down to 50 ºC, the gas was switched to 5% H2/Ar flow (30 mL min-1) and the sample

is heated to 800 ºC at a heating rate of 10 ºC min-1. The signal was recorded by a thermal

conductivity detector (TCD).

In situ DRIFTS experiments were performed in an in situ reaction cell on a Bruker VERTEX

70 spectrometer with a narrow band MCT detector. Each spectrum was collected by 32 scans at a

resolution of 4 cm-1. Before measurement, the sample was reduced in 10% H2/Ar flow (30 mL

min-1) at 400 ºC for 1 h, and then purged with Ar at 400 ºC for 1 h. The catalyst was subsequently

cooled down to the desired temperature to obtain the background spectrum. The CO2

hydrogenation reaction was carried out at a temperature region of 50-250 ºC in H2/CO2 (3:1) flow

of 30 mL min-1 at a total pressure of 0.3 MPa. The CO adsorption was performed at 30 ºC after

5% CO/Ar adsorption for 30 min and Ar purge for 1 h.

Catalytic testing. The catalytic testing was carried out on a continuous-flow, high-pressure,

tubular fixed-bed reactor (internal diameter of 8 mm). 0.2 g catalyst (40-60 mesh) was diluted with

0.4 g quartz sand (40-60 mesh) and then loaded into the stainless steel tube. Before measurement,

the catalyst was reduced in 10% H2/Ar flow of 30 mL min-1 at 400 ºC for 1 h. After cooling down

to 150 ºC, the feeding gas with a H2/CO2 ratio of 3 was introduced into the reactor and pressurized

to 4.5 MPa. The reactant gas flow was set as 36 mL min-1 and the reaction temperature was raised

to the desired temperature (200-360 ºC). The post-reactor lines and valves were heated and kept at

150 ºC to avoid product condensation. The products were analyzed online by a gas chromatograph

6
equipped with a thermal conductivity detector. The CO2 conversion and product selectivity were

calculated using an external standard method. All data were obtained after the reaction was stable

for 2 h.

Results and discussion

The structural features of Cu-doped catalysts

A series of Cu-doped ZnZrOx solid solution catalysts were prepared by a coprecipitation method

(see Experimental section). The Zn/Zr atomic ratio was set at a constant of 13/87 and the molar

content of Cu in total metals varied from 0 to 2%. For un-doped ZnZr solid solution, the bulk

structure is mainly tetragonal ZrO2 (t-ZrO2) while the surface layer is a transition state between

monoclinic ZrO2 (m-ZrO2) and tetragonal ZrO2 phases (Fig. 1a and 1b).18 The lattice contraction

of t-ZrO2 and the absence of ZnO in the ZnZr sample (Fig. 1a and Fig. S1) support that Zn2+ is

incorporated into the lattice of ZrO2 to form ZnZrOx solid solution.18,21 When a small amount of

Cu is introduced, the crystal structure of ZnZrOx is almost unchanged but the full width half

maximum (FWHM) increases from the XRD analysis (Fig. 1a), which suggests a decrease in the

crystalline size of ZnZrOx particles and thus leading to the increase of BET surface area (Table

S1). It is noted that even 0.2% Cu can greatly increase the catalyst surface area from 53 m2 g-1

(ZnZr) to 90 m2 g-1 (0.2% CuZnZr). Then it gradually goes up to 117 m2 g-1 when 2% Cu is doped.

Moreover, we do not find the diffractions or lattice fringes of CuOx (Fig. 1a and 1c, Fig. S1 and

S2), suggesting that Cu is highly dispersed. After Cu doping, the diffraction peak at 30.6º (ZnZr)

slightly shift to 30.5º (CuZnZr), along with the color change from white to green with increasing

Cu dosage (Fig. S1 and Fig. S3), suggesting the doping of Cu2+ ions into ZrO2 to form CuxZryOz

7
solid solution.38,39 TEM images in Fig. S4 show that the structure of CuZnZr catalyst is composed

of numerous particles by packing, forming abundant interparticle pores (Table S1).

When the catalysts are reduced under H2/Ar flow at 400 ºC, surface segregation would take

place. The actual surface concentrations of Cu and Zn are both greater than theoretical values (Fig.

1d and Table S2), which indicates that Cu and Zn are more likely to migrate to the surface of

catalyst upon reduction. As the content of surface Cu increases, the surface content of Zn decreases

from 20.1% to 17.3 % while the bulk content of Zn only decreases by 0.26% (Fig. 1d and Table

S2). Considering that the surface concentration of Zr4+ changes very little (Table S2), we speculate

that Cu atoms partially replace the position of Zn atoms on the surface of reduced catalyst. XPS

spectra of reduced CuZnZr samples show the binding energy of Cu is ascribed to low-valance Cu

(Cu0 or Cu+) species, and that of Zn belongs to partially reduced ZnO (Fig. S5). Note that we could

not find the presence of metallic Cu particles or clusters in the HRTEM images of the reduced

0.5% CuZnZr sample (Fig. S6), we speculated that the Cu is highly dispersed in the ZnZrOx

solution. Actually, the HAADF-STEM elemental mapping analysis (Fig. 1e) further confirms the

homogeneous distribution of Cu in the tens of nanometer scale.

8
Fig. 1. (a) PXRD patterns of fresh x% CuZnZr samples. HR-TEM images of fresh (b) ZnZr and

(c) 0.5% CuZnZr. (d) Surface fraction of Cu and Zn in different reduced x% CuZnZr samples

measured by XPS. (e) HAADF-STEM image and the corresponding element mapping of the

representative 0.5% CuZnZr sample after H2 reduction.

DRIFTS spectra of CO adsorption were performed to explore the chemical state of Cu on the

surface of reduced CuZnZr samples. As shown in Fig. 2a, the band at 2080-2120 cm-1 is assigned

to CO chemisorption on Cu sites. It gradually intensifies as the content of Cu increases, which

means the increasing number of surface Cu sites. When the content of Cu is less than 1%, the band

at 2095 cm-1 is quite close to the CO adsorption on metallic Cu (Cu0) of Cu-ZnO catalysts.40-42

This indicates the existence of Cu-Zn interactions on the Zn-rich surface of solid solution.

However, as the content of Cu increases to 2%, the peak slightly blue shifts, suggesting the

9
reduction of back donating electrons from Cu to CO. Considering the decrease in the surface

content of Zn with Cu addition, we think that the excess Cu doping leads to the weakening of Cu-

Zn interactions which is further confirmed by a control experiment. Increasing the Zn content at a

fixed Cu/Zr molar ratio leads to the increase of CO adsorption on metallic Cu caused by the Zn

modification via electron transfer (Fig. S7 and S8).

H2-TPR experiments were performed to study the reducibility of x% CuZnZr catalysts and the

interactions between different components. As showed in Fig. 2b, the reduction peaks can be

divided into two regions. The peaks before 350 ºC are assigned to the reduction of Cu-O species

along with segregation of Cu upon reduction, while the reduction temperature above 350 ºC is for

ZnZrOx. As for the 0.2% CuZnZr sample, there are no reduction peaks of CuO because the content

of Cu is too low. When the Cu content reaches 0.5%, a broad reduction peak at 290 ºC appears,

corresponding to the reduction of Cu-O species. The Cu2+ cations are difficult to be reduced in this

system due to the strong interactions between Cu2+ and ZnZrOx by forming CuxZryOz solid

solution.38 As the content of Cu further increases to 1% and 2%, the main reduction peak shift to

lower temperature (252 ºC), suggesting the slight weakening of Cu-ZnZrOx interactions.43,44 As

for the high temperature region, the un-doped ZnZr sample has a reduction peak at 455 ºC which

is attributed to the reduction of surface species of ZnZrOx solid solution.18 With the introduction

of Cu, the reduction peak of surface ZnZrOx shifts towards lower temperature (400 ºC),

demonstrating the existence of hydrogen spillover on the surface of Cu doped ZnZrOx catalysts.

XRD pattern of the representative 2% CuZnZr sample after TPR treatment does not show clear

diffractions for metallic Cu (Fig. S9), further supporting that Cu is highly dispersed and strongly

trapped by ZrO2.

10
Fig. 2. (a) DRIFTS spectra of CO adsorption on the reduced x% CuZnZr catalysts and (b) H2-TPR

results of the fresh x% CuZnZr catalysts.

Catalytic performance of CuZnZr catalysts

The performance of each catalyst was evaluated at 230-360 ºC and 4.5 MPa. Before the CO2

hydrogenation testing, the catalysts were activated in H2/Ar flow at 400 ºC for 1 h. As shown in

Fig. 3, the ZnZr catalyst exhibits high methanol selectivity (> 70%) in a wide range of reaction

temperatures (260-330 ºC). But the activity is still very low (CO2 conversion < 10%) below 330

ºC. Notably, the activity of CO2 hydrogenation goes up with the addition of Cu. In Fig. 3a, as the

content of Cu increases, the overall curves of CO2 conversion shift to the lower temperature region.

Precisely, the CO2 conversion of 0.2% CuZnZr, 0.5% CuZnZr and 2% CuZnZr samples are 2.9,

4.5 and 5.9 times that of ZnZr at 290 ºC (Table S3). As for the selectivity to methanol and CO, all

samples show the same variation tendency that the methanol selectivity decreases while CO

selectivity increases as the temperature increases (Fig. 3b and Fig. S10). Moreover, the Cu doping

11
leads to a decline of methanol selectivity (Fig. 3b). But when the Cu content is less than 0.5%, the

methanol selectivity remains almost unchanged (80.5% vs 76.0%) at 290 ºC (Table S3). As for the

methanol yield (Fig. 3c), all samples exhibit a volcanic relationship between methanol yield and

reaction temperature. The methanol production rate is limited by kinetics at low temperature and

by thermodynamics at high temperature due to the exothermal nature of methanol synthesis. Table

S3 compares the methanol yield over ZnZr, 0.2% CuZnZr, 0.5% CuZnZr, 1% CuZnZr and 2%

CuZnZr at 290 ºC. It increases by 2.8, 4.2, 4.4 and 4.0 times from 1.70% to 4.71%, 7.20%, 7.47%

and 6.88%, respectively. Note that when trace Cu (< 0.5%) is used, the CO2 conversion is greatly

improved without changing methanol selectivity too much (76.0%~80.5%). Further increasing Cu

content boosts the RWGS reaction and hence the methanol selectivity drops quickly. Fig. 3d shows

the CH3OH selectivity as a function of CO2 conversion. We can find that ZnZr, 0.2% CuZnZr,

0.5% CuZnZr and 1% CuZnZr catalysts exhibit similar tendency that the CH3OH selectivity

markedly decreases when the CO2 conversion is above 12%. Generally, there is always a seesaw

effect between methanol selectivity and CO2 conversion. It is noted that 0.5% CuZnZr shows the

highest methanol selectivity at a fixed CO2 conversion (6%~14%) among all the tested catalysts.

We next compare the catalytic activities of these catalysts at 290 ºC before thermodynamic

equilibrium of methanol synthesis. As shown in Fig. 3e, the CO2 conversion increases

monotonously with increasing Cu content while the CH3OH selectivity shows the opposite trend.

As a result, the methanol yield initially increases quickly as the Cu content increase to 0.5% and

then reaches a platform at around 7%. Considering that the surface area can also affect the activity

by exposing more active sites, we then normalize the methanol formation rate by BET surface area

to compare the intrinsic activities of catalysts in a fair way. It is clearly found that 0.5% CuZnZr

and 1% CuZnZr show higher CH3OH formation rate than the others (Table S3). In terms of

12
methanol yield and selectivity, we believe the 0.5% CuZnZr catalyst is a very good candidate for

selective and efficient CO2 hydrogenation to methanol (comparable to the reported advanced oxide

catalysts listed in Table S4). It performs a methanol yield of 7.2% with high methanol selectivity

of 76.0% at 290 ºC. It also exhibits long-term stability in a 100 h time-on-stream test (Fig. 3f).

Moreover, the lattice fringes of Cu are still absent in HR-TEM images over the 0.5% CuZnZr

sample after CO2 hydrogenation (Fig. S11), indicating the good stability benefited by the strong

interaction between Cu and metallic oxide.

Fig. 3. (a) CO2 conversion, (b) CH3OH selectivity, (c) CH3OH yield and (d) CH3OH selectivity as

a function of CO2 conversion over different x% CuZnZr catalysts. (e) Catalytic performance of

various catalysts at 290 ºC. (f) Time-on-stream (TOS) test of the 0.5% CuZnZr catalyst at 290 ºC.

Reaction conditions: 0.2 g catalyst, 4.5 MPa, CO2/H2 = 1/3, 36 mL min-1.

13
Mechanism study on the promotion of Cu in methanol synthesis

In situ DRIFTS experiments were then performed to identify reaction intermediates on the

catalyst surface under CO2/H2 atmosphere. Fig. 4 and Fig. S12 illustrate the changes of IR spectra

of the CO2+H2 reaction on ZnZr and 0.5% CuZnZr at different reaction temperatures. Both

catalysts show very similar bands, suggesting the same intermediates and adsorption sites. Table

1 lists the assignments of the IR bands after a control experiment over pure ZrO2 and ZnO samples

(Fig. S13). Precisely, bidentate bicarbonate (HCO3-Zr, 1632 cm-1) and bidentate carbonate (CO3-

Zr, 1300 cm-1) adsorbed on Zr sites are the primary species at 50 and 100 ºC (Fig. 4b and 4c). They

convert to HCOO* on the surface of ZrO2 (HCOO-Zr, 2980, 2884 and 1591 cm-1) at 150 ºC (Fig.

4a and 4b). As the temperature is raised to 200 ºC, the amount of HCOO* increases and CH3O*

(H3CO-Zr, 2932 and 2824 cm-1) is produced at the same time (Fig. 4a). Neither gas CO nor

adsorbed CO is detected at 200 ºC (Fig. S12), suggesting that methanol synthesis is more likely to

experience a HCOO*-intermediated pathway. The conversion step of HCOO* to CH3O* (e.g.,

HCOO* → HCOOH* → H2COOH* → H2CO* → CH3O*) encounters a high energy barrier and

the corresponding bottleneck is generally associated with the hydrogenation reactions of HCOO*

and HCOOH*.46 High temperature is favorable for this key step. Further increasing the reaction

temperature to 250 ºC, the amount of CH3O* significantly increases while that of HCOO* slightly

decreases, revealing an accelerated transformation of HCOO* to CH3O*. Regarding the effect of

Cu, the amount of HCOO* and CH3O* both increase after 0.5% Cu doping at 150~250 ºC. More

importantly, the amount of CH3O* over 0.5% CuZnZr is much greater than that over ZnZr at 250

ºC. This demonstrates that even a small dosage of Cu can greatly promote the formation of CH3O*,

well consistent with the above-mentioned improved activity (Fig. 3e).

14
Fig. 4. In situ DRIFTS spectra of ZnZr and 0.5% CuZnZr at different temperatures in the range of

(a) 3050-2700 cm-1, (b) 1750-1450 cm-1 and (c) 1420-1000 cm-1.

Table 1. DRIFTS peak assignments of the surface species for CO2 + H2 reaction

Peaks (cm-1) Assignment Species References

1630-1635 νas(OCO) 36
HCO3-Zr
1225 νs(OCO) 45
1500-1520 νas(OCO) 11, 12, 45
CO3-Zr, CO3-Zn
1420-1430, 1298-1340 νs(OCO) 11, 12, 46, 47
2970-2980 δ(CH)+ νas(OCO)
2875-2885 ν(CH)
2730-2740 δ(CH)+ νs(OCO) HCOO-Zr 11, 12, 18, 45
1585-1595 νas(OCO)
1370-1385 δ(CH)
2925-2945 νas(CH3)
2820-2825 νs(CH3) H3CO-Zr 11, 12, 18, 45
1140-1145, 1045-1050 ν(CO)

15
 Temporal resolution spectra were collected to study the dynamic behavior of surface reaction

intermediates over ZnZr and 0.5% CuZnZr. As shown in Fig. 5a, 5b and Fig. S14, the bands change

with reaction time going on, supporting a reaction process of CO2 → CO3*/HCO3* → HCOO* →

CH3O* → CH3OH. The formation of HCOO* is a kinetically fast process while its hydrogenation

to CH3O* is more difficult, which relies on the hydrogenation ability of catalyst. The bands at

2878 and 2824 cm-1 are chosen to study the dynamic changes of HCOO* and CH3O* at 200 ºC

(Fig. S14f) and 250 ºC (Fig. 5c). Both of the intermediates initially increase very fast and then

gradually approach an equilibrium. The addition of 0.5% Cu promotes both the generation rate

and equilibrium concentration of HCOO* and CH3O*. The formation of HCOO* is regarded as a

process of nucleophilic attack of H* towards activated CO2*, which could be enhanced by the

increased H* coverage degree brought by Cu. As for metallic oxides catalyzed methanol synthesis,

H2 activation plays a key role in CO2 conversion.19,33 Cu has strong hydrogenation capability when

compared to oxides (e.g., ZnO and ZrO2). As for CH3O*, its formation would profit from the

improved coverage degree of HCOO* and H*. We believe that the promotion of Cu is attributed

to the hydrogen spillover effect.

We also measured the ratio of CH3O* to HCOO* to understand the promotion effect of Cu. At

200 ºC, the CH3O*/HCOO* ratio increases gradually with reaction time over both ZnZr and

CuZnZr, suggesting that the transformation of HCOO* to CH3O* is limited by the reaction

temperature which leads to low formation rate of CH3OH. There is not much difference in the ratio

after Cu doping. When increasing the temperature to 250 ºC, the CH3O*/HCOO* ratios over two

catalysts reach equilibrium quickly (Fig. 5d). Note that the equilibrium CH3O*/HCOO* ratio over

0.5% CuZnZr is greater than that over un-promoted ZnZr catalyst, indicating that the reaction rate

constant of HCOO* → CH3O* is boosted by Cu doping. In fact, the step of HCOO* hydrogenation

16
to CH3O* requires high activation energy, hence its reaction rate constant would be more sensitive

to reaction temperature than other steps. We believe that the addition of Cu increases the amount

of active hydrogen atom for nucleophilic addition to HCOO* to produce CH3O* and eventually

facilitate the synthesis of methanol.

Fig. 5. Dynamic DRIFTS spectra of CO2+H2 reaction at 250 ºC over (a) ZnZr and (b) 0.5%

CuZnZr. (c) Variation of IR peak intensities of HCOO* (2878 cm-1) and CH3O* (2824 cm-1) at

250 ºC. (d) Dynamic change of the CH3O*/HCOO* ratio over ZnZr and 0.5% CuZnZr at 200 and

250 oC.

17
 To further prove the positive role of hydrogen spillover in methanol synthesis, we compared the

catalytic performance of trace (0.02%) metal-modified ZnZrOx solid solution such as PdZnZr, and

PtZnZr. As shown in Fig. 6a and Table S5, the CO2 conversion increases by several times before

the thermodynamic control of methanol synthesis. As for the product selectivity, all the samples

show the similar methanol and CO selectivity (Fig. 6b and 6c). This suggests that the doping of

trace metals have almost no influence on product distribution. The methanol yield has been greatly

improved with the addition of trace amounts of metals, especially at low temperatures (Fig. 6d).

The PdZnZr and PtZnZr samples both show comparable methanol yield (4.58% and 4.31%) at 290

ºC compared to CuZnZr (4.14%), which is more than two times that of un-doped ZnZr catalyst.

H2-TPR results are shown in Fig. S15. The reduction peak of surface species of ZnZrOx solid

solution from 455 ºC shifts to 402 ºC on PdZnZr and 415 ºC on PtZnZr, proving the existence of

hydrogen spillover on the surface of Pd or Pt doped ZnZrOx catalysts. The hydrogen spillover

effect can greatly promote the H2 activation, hence enhancing CO2 conversion. All these results

demonstrate the important impact of H2 activation on CO2 hydrogenation to methanol.

18
Fig. 6. (a) CO2 conversion, (b) CH3OH selectivity, (c) CO selectivity and (d) CH3OH yield over

0.02% MZnZr (M=Cu, Pd, Pt) catalysts. Reaction conditions: 0.2 g catalyst, 4.5 MPa, 260-320 ºC,

CO2/H2 = 1/3, 36 mL min-1.

As mentioned above, doping Cu can greatly increase the hydrogenation ability of CuZnZr

catalysts, which contributes a lot to the total CO2 conversion. As shown in Scheme 1, the ZnZr

catalyst exhibits high methanol selectivity of 80.5%, but the relatively inefficient H2 activation on

Zn sites leads to low methanol yield at 290 ºC. With the introduction of 0.5% Cu, the ordered

structure of Cu doped ZnZrOx still keeps the advantage of high methanol selectivity, hence the

methanol selectivity does not change much, but the methanol yield is significantly improved by

19
more than 300%. The methanol synthesis reaction is kinetically more complicated (with several

elementary reactions) than CO production. Hydrogen spillover can easily take place from Cu to

ZnZr oxide sites. The improved hydrogenation capability can greatly accelerate the conversion of

HCOO* to CH3O* (bottleneck in methanol synthesis), thus promote the yield of methanol.

Considering that RWGS reaction is also facilitated when introducing excess Cu, we at last screened

out the 0.5% CuZnZr catalyst as a good candidate for methanol synthesis, which exhibits a high

methanol yield (7.2%) at a reasonably high selectivity of 76% at 290 ºC.

Scheme 1. Schematics of the role of Cu in methanol synthesis from CO2 hydrogenation over two

representative ZnZr and 0.5% CuZnZr catalysts. S represents methanol selectivity and Y stands

for methanol yield.

Conclusions

In summary, we have synthesized a series of CuZnZrOx ternary metallic oxide solid solution

catalysts with improved activity for CO2 hydrogenation to methanol. As the molar percent of Cu

increases to 0.5%, the CO2 conversion increases to 9.5% and the methanol yield is improved to

7.2% with comparable methanol selectivity and long-term stability at 290 ºC. The promoted

20
activity is attributed to the enhancement of hydrogenation capacity and accelerated transformation

of HCOO* to CH3O* caused by hydrogen spillover effect, which is proved by H2-TPR and in situ

DRIFTS analysis. The great role of hydrogen spillover effect is also demonstrated by the improved

activity on PdZnZr and PtZnZr catalysts. However, excess Cu doping leads to a sharp decrease in

methanol selectivity. We propose that the ordered ZnZr solid solution structure and highly

dispersed Cu doping are crucial to high methanol selectivity and yield. We believe that this work

highlights the impacts of increased H2 dissociation capability and solid solution structure on highly

active and selective synthesis of methanol from CO2 hydrogenation over metallic oxide catalysts.

ASSOCIATED CONTENT

21
Supporting Information.

Supplementary figures and tables are described in Supporting Information.

AUTHOR INFORMATION

Corresponding Author

* E-mail: liugl@[Link].

* E-mail: hongxl@[Link]

Notes

The authors declare no competing financial interest.

ACKNOWLEDGMENT

This work is financially supported by the National Natural Science Foundation of China

(21872106) and the Fundamental Research Funds for Central Universities (2042019kf0019).

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29
Graphical Abstract

30
Highlights

Cu atoms are highly dispersed on the surface of ZnZrOx solid solution.

Trace of Cu doping improves methanol formation rate via hydrogen spillover effect.

The ordered structure of ZnZrOx solid solution keeps high methanol selectivity.

The strategy of hydrogen spillover can also be applied to Pd or Pt doping to ZnZrOx.

31
Declaration of interests

☒ The authors declare that they have no known competing financial interests or personal
relationships that could have appeared to influence the work reported in this paper.

☐The authors declare the following financial interests/personal relationships which may be considered
as potential competing interests:

32