1 s2.0 S2352186423002134 Main

Environmental Technology & Innovation 31 (2023) 103217
Contents lists available at ScienceDirect
Environmental Technology & Innovation

journal homepage: www.elsevier.com/locate/eti
Unlocking the potential of CO2 hydrogenation into valuable

products using noble metal catalysts: A comprehensive review
Muhammad Tawalbeh a,b , Rana Muhammad Nauman Javed c ,
∗
Amani Al-Othman c , Fares Almomani d , , Saniha Ajith d
a
Sustainable and Renewable Energy Engineering Department, University of Sharjah, PO. Box 27272, Sharjah, United Arab Emirates
b
Sustainable Energy & Power Systems Research Centre, RISE, University of Sharjah, P.O. Box 27272, Sharjah, United Arab Emirates
c
American University of Sharjah, Department of Chemical Engineering, PO. Box 26666, Sharjah, United Arab Emirates
d
Department of Chemical Engineering, Qatar University, Qatar
article info a b s t r a c t
Article history: The research towards the development of alternative fuel generation technologies has
Received 10 April 2023 been triggered by Climate change, global warming, and the ongoing depletion of fossil
Received in revised form 18 May 2023 fuels. The hydrogenation of carbon dioxide (CO2 ) into methanol, dimethyl ether, carbon
Accepted 18 May 2023
monoxide, and value-added products appears to be a promising path to mitigate CO2
Available online 25 May 2023
emissions. The role of noble metal catalysts (Pt, Pd, Rh, Au, etc.) in CO2 conversion
Keywords: into useful products has been addressed in this work. The literature reported improved
Added value products catalytic performance of the reverse water-gas shift (RWGS) reaction, and several studies
Nano-catalysis were examined for the optimal performance in CO2 hydrogenation processes. The focus
Reaction pathways was on the preparation techniques, supporting materials, noble metals loading, and
Yield reactions mechanism. This paper shows the most notable results in the application of
Selectivity noble metals and demonstrates an enhanced CO2 conversion of 80% and CO selectivity of
Enhanced conversion process
>99%. Furthermore, this review demonstrated the promising role of Au-based catalysts in
improving the kinetics of the CO2 hydrogenation reaction with 80% methanol selectivity
when nano-sized zinc oxide particles were involved. Recently, CO2 hydrogenation with
photothermal catalysis resulted in a high methane yield and selectivity of 100%. Notable
research paths were directed toward the investigation of Au and Pd-based catalysts and
exploited them to produce formats compounds with promising conversion. Furthermore,
the synthesis of heterogeneous oxide-zeolite (OX-ZEO) bi-functional catalysts for im-
proved CO2 hydrogenation can be explored in reactors powered by renewable energy
sources.
© 2023 The Author(s). Published by Elsevier B.V. This is an open access article under the CC
BY license (http://creativecommons.org/licenses/by/4.0/).
Contents
1. Introduction............................................................................................................................................................................................... 2
2. Outline of CO2 hydrogenation via catalysis .......................................................................................................................................... 3
3. Catalytic processes for CO synthesis via RWGS reaction .................................................................................................................... 3
3.1. The mechanism of surface redox reactions .............................................................................................................................. 4
3.2. The associative mechanism: concept and background ........................................................................................................... 4
4. Noble metal catalysts for reverse water-gas shift reactions............................................................................................................... 6
5. Noble metal-based catalysts: Types and potential............................................................................................................................... 9
∗ Correspondence to: Department of Chemical Engineering, Qatar University, P.O. Box: 2713 Doha, Qatar.
E-mail address: falmomani@qu.edu.qa (F. Almomani).
https://doi.org/10.1016/j.eti.2023.103217
2352-1864/© 2023 The Author(s). Published by Elsevier B.V. This is an open access article under the CC BY license (http://creativecommons.org/
licenses/by/4.0/).
M. Tawalbeh, R.M.N. Javed, A. Al-Othman et al. Environmental Technology & Innovation 31 (2023) 103217
6. Noble metal catalysts: advantages and drawbacks .............................................................................................................................. 11

7. Advancement in catalytic hydrogenation .............................................................................................................................................. 12
8. Conclusions and prospects ...................................................................................................................................................................... 12
CRediT authorship contribution statement ........................................................................................................................................... 13
Declaration of competing interest.......................................................................................................................................................... 13
Data availability ........................................................................................................................................................................................ 13
Acknowledgments .................................................................................................................................................................................... 13
References ................................................................................................................................................................................................. 13
1. Introduction
The synergic increased carbon dioxide (CO2 ) emissions into the environment are the outcome of the drastic consump-
tion of fossil fuels to maintain the energy demand/supply. Despite major environmental issues frequently linked to CO2
emissions, fossil fuels are considered the major source of energy supply for the foreseeable future (Sodiq et al., 2023).
The CO2 emissions are the principal contributor to air pollution and global warming (Chishti et al., 2020; Tawalbeh et al.,
2021a). The CO2 emission has been forecasted up to 1750 MtCO2 ,with more than a 90% confidence interval of 1703 MtCO2
and 1796 MtCO2 , for 2030 (Gurbanov et al., 2023). The 21st century has witnessed the universal issue of rising CO2 levels,
which contribute to the increase in global temperatures and affects all areas of human life and the environment (Tawalbeh
et al., 2022a). In the years 2019–2020, CO2 emissions from fossil fuels reportedly declined by 5.4% (Tollefson, 2021). There
is a collective global urge to achieve a net zero carbon economy for the mitigation of overall climatic change. To achieve
this, unique approaches must be formulated to build a net zero carbon economy across all sectors (Buckingham et al.,
2022). In 2015, UN Climate Change Conference (COP21-Paris) was led by global climate experts in which they collectively
agreed to adopt steps to combat climate change, with the ultimate objective of limiting global temperature rise to below
2 ◦ C (Peter, 2018).
Several innovative and research-based engagement strategies have been investigated to achieve environmental sus-
tainability and combat global warming (González-Gómez et al., 2022; Dai et al., 2022). The aqueous amine-based chemical
absorption (Zahedi et al., 2022), which typically consists of a CO2 absorber, regenerator, and cross-heat exchanger, was one
of the first technologies to capture carbon from power plants. High energy consumption and large capital manufacturing
costs are associated with this technology, making it a less feasible option (Jiang et al., 2023a). Lately, carbon capture and
storage (CCS) technologies (Alami et al., 2020; Kim et al., 2022b) have shown promising potential for CO2 emissions.
This technology is highly dependent on operating variables, such as the combustion process, separation techniques,
cost of transportation, and long-term storage (Alami et al., 2020). Another equally effective strategy to minimize carbon
emissions is the CO2 capture, utilization, and storage (CCUS) technologies, which convert CO2 into value-added products
and alternative fuels utilizing renewable energy sources and using generation materials (Dat Vo et al., 2022; Pan et al.,
2022; Yusuf and Almomani, 2023; Alami et al., 2021), such as ionic liquids (Lian et al., 2021; Faisal Elmobarak et al.,
2023), nanostructured composite catalysis (Almomani et al., 2019), and metal–organic frameworks (Jing et al., 2018;
Fan and Tahir, 2022). The potential application, such as absorption/adsorption, and membrane/cryogenic separation with
utilization technologies (physical/chemical/biological utilization), has exhibited their significance for alleviating the CO2
issue (Fu et al., 2022). Industrial carbon capture could be classified into systems, i.e., pre/post-combustion, followed by
the oxy-fuel and chemical loop combustion (Fennell et al., 2021). Captured carbon has been investigated as an excellent
source to produce alternative and sustainable fuels, such as synthesis gas (syngas). Furthermore, captured CO2 could be
used in various chemical industries to produce fuels and valuable chemicals, namely, aromatics, olefins, carboxylic acids,
alcohols, and aldehydes (Velty and Corma, 2023).
The CO2 hydrogenation is a promising mechanism to convert waste to wealth and increase energy storage efficiencies.
The CO2 reduction to other products can be achieved via electrochemical (Wang et al., 2019), photochemical (Fan and
Tahir, 2022; Du et al., 2020; Almomani et al., 2023), and thermochemical (De et al., 2020) catalysis. The method of
choosing the ideal process and catalyst depends on the reactions employed. For instance, in thermochemical catalysis, the
catalyst needs to maintain stability and structural integrity at very high temperatures (Tawalbeh et al., 2021b). Similarly,
in the electrochemical route, the catalyst must be able to counter the production of H2 , and in photochemical catalysis, an
appropriate material, such as a semiconductor must be chosen (Peter, 2018). Amongst the mentioned pathways, thermos-
catalysis is a promising process due to the enhanced reaction kinetics and active center availability in CO2 reduction
mechanisms. Stable molecules require a great amount of activation energy; therefore, species that possess larger ∆G are
more exposed to enhanced conversion than electro-catalysis or photo-catalysis.
To the best of the author’s knowledge, this is the most recent and comprehensive review work of the advancements
on noble metallic catalysts for CO2 hydrogenation. The paper focuses on critically summarizing the novel developments
of noble metallic catalysts for the modified structural properties for improved CO2 conversion, attributed to enhanced
catalytic activities. The novel achievements of heterogeneous catalysts for alternative methanol and dimethyl ether (DME)
production have been discussed via CO2 hydrogenation. One of the main applications of methanol fuel is in automobiles
and in fuel cells (Tawalbeh et al., 2022b). While DME could be used to balance the supply and demand of diesel
with outstanding efficiency and low nitrogen oxides and sulfur oxides emissions Channiwala et al. (2017). A thorough
2
Fig. 1. A schematic outline of mechanisms for catalytic CO2 hydrogenation.
investigation of the activity and surface morphology of noble catalysts with catalytic supports has also been conducted.
The optimal loading and their enhanced impact on catalytic performance, and reaction processes were described. The
cause of the high conversion of CO2 was outlined with the help of improved catalyst stability, attributed to the interaction
between catalyst active sites and support structures.
2. Outline of CO2 hydrogenation via catalysis
At present, the ‘Carbon Recycling International’ (CRI) plant in Iceland can produce 4000 tons/year of methanol from
CO2 (Zhong et al., 2020). Effective and stable catalysts are needed for the conversion to C2+ valuable products. The C–C
linkage activity is quite unstable and the catalyst deactivates in the presence of a by-product (water) (Guo et al., 2018).
The hydrogenation of CO2 using homogenous/ heterogeneous catalysts for the sustainable and alternative production of
products/chemicals, such as DME, methanol, hydrocarbons, formic acid, olefins, and carbon monoxide have been discussed
in detail by Wang et al. (2011) and Li et al. (2018). Fig. 1 outlines the mechanisms for catalytic CO2 hydrogenation
to different products. The reverse water-gas shift reaction (RWGS) converts the catalytic CO2 to CO via hydrogenation,
which can be further utilized for the value-added products. These technologies primarily include the ‘Sabatier-Senderens
methanation’ for methane production, ‘syngas reaction’ for methanol production (Pan et al., 2020), ‘methanol dehydration’
for DME synthesis, and ‘Fischer Tropsch’, which is a process that involves the production of hydrocarbons via the catalyzed
conversion reaction of carbon monoxide and hydrogen.
Two efficient strategies have been considered for the conversion of CO2 to C2+ hydrocarbons. The first strategy is
combining RWGS reaction with the Fischer–Tropsch synthesis (FTS), and the second involves methanol synthesis at an
elevated temperature over bi/multifunctional catalysts (Gao et al., 2020). The production of undesired CO during CO2
hydrogenation by RWGS is a challenging component of the synthesis of methanol (Tawalbeh et al., 2023). This challenge
can be combated by either lowering reaction temperature to favor exothermal reaction or increasing space velocity to
decrease CO selectivity (Gao et al., 2020).
Water serves as an inhibitor and lowers catalytic activity, which results in inefficient CO2 conversion and a small yield.
According to Le-Chatelier’s principle, this problem could be resolved by removing water molecules from the catalyst’s
active sites. It may be possible to remove water using hydrophilic sorbents or permeable membranes, provided that the
membranes are routinely cleaned to maintain their mechanical and thermal stability (Zhang et al., 2022; Junaidi et al.,
2021; Tawalbeh et al., 2018). To tackle the water issues in reactors, two strategies have been used in literature: intensified
sorption-enhanced reaction process (SERP) and reactive adsorption. The former technique is a common membrane
technology with reactive vapor permeation. These techniques can greatly lower the deactivation of the catalyst while
maintaining excellent product selectivity (van Kampen et al., 2019).
The optimal design/choice of catalysts has a remarkable contribution to the selectivity/quality of methanol and DME.
For increased output, factors, such as reaction processes, reactor design, ideal operating conditions, thermodynamics, and
metal-based catalyst performance must all be taken into account (Vu et al., 2021).
3. Catalytic processes for CO synthesis via RWGS reaction
An endothermal RWGS has been mentioned as shown in Eq. (1) for the CO2 hydrogenation to CO (Stangeland et al.,
2017):
Catalyst
CO2 + H2 ⇐⇒ CO + H2 O ∆H0298K = +41.0 kJ/mol (1)
3
Being an endothermic RWGS reaction, increasing temperatures up to 750 ◦ C can increase CO2 transformation and CO
selectivity by 70% and 99%, respectively (Yang et al., 2020). Engineering stable catalysts for effective CO2 conversion at
high temperatures with improved activity is a challenging process. This implies that the performance of the catalyst has
a significant impact on the selectivity of methane and alcohols or hydrocarbons. The potential for catalyst deactivation
at high temperatures as a result of metal sintering and coke depositions presents another difficulty (Belekar, 2021; Liu
et al., 2022a). The Pd, Pt, Rh, and Ru are four of the most extensively researched noble metal catalysts, have demonstrated
an exceptional affinity for methanation from CO2 (Pakhare and Spivey, 2014). New noble metal catalyst advancements,
synthesis mechanisms, and catalytic structural supports for the best performance are the main topics of the following
sections. Moreover, surface redox and associative mechanisms have been discussed for RWGS reaction, which results
significantly in the production of various by-products.
3.1. The mechanism of surface redox reactions
The surface redox is one of the most used mechanisms to describe CO2 hydrogenation. This mechanism involves CO
adsorption on a metal site, CO oxidation by oxygen atoms, and CO reoxidation by water molecules. These mechanisms
are the primary contributors to the RWGS reaction, which would have a significant impact on CO2 /H2 intakes and
thus the hydrogenation process. Pd, Co, Ni, Fe/ceria, and Pd/silica were used in a comparative investigation of surface
redox mechanisms by Hilaire et al. (2001). Among these catalysts, Pd/ceria demonstrated the highest activity and was
significantly more active than the other catalysts. The catalyst followed a zeroth-order rate for the optimal adsorption of
CO due to the saturation of Pd surfaces. The experimental studies revealed the formation of carbonate species on ceria
during reduction by CO on Pd/ceria, as well as during water-gas shift reaction (WGSR). This demonstrates that reoxidation
of O2 or H2 O can be employed to remove carbonate.
Wang et al. (2013) showed that the quantitative temporal analysis of products (TAP) measurements could be used
to study the activity and redox mechanism of Au/CeO2 during the catalytic conversion of CO2 . The active surface of O
on Au/CeO2 was increased by 24%–30% at 180–300 ◦ C. Dostagir et al. (2023) showed an increased 99% CO selectivity
with high yield from the redox mechanism over the reducible interface of In-TiO2 mixed oxide and reported a promoter-
free oxide catalyst for CO2 hydrogenation. Ferri et al. (2002) discussed CO2 hydrogenation over the solid–liquid Pt/Al2 O3
catalyst in cyclohexane via redox mechanisms and tested the outcome using in situ attenuated total reflection (ATR)
infrared spectroscopy. The obtained spectrum revealed a linear relationship of low vibrational frequencies with bonded
CO molecules. The redox mechanism of the Pt/Al2 O3 model is presented in Fig. 2(a).
Ai et al. (2022) used wet impregnation and grinding methods to design catalyst consisting of Cu supported on γ -Al2 O3 .
The presence of Cu showed an impact on the Cuo crystallinity and adsorption/activation of CO2 molecules on Cu/γ -Al2 O3 ,
resulting in an increased reaction rate of 2.12 × 10−5 mol (gcat s)−1 at 400 ◦ C via redox mechanism. Fig. 2(b) illustrates
the redox mechanism on xCuAl catalyst (Ai et al., 2022).
3.2. The associative mechanism: concept and background
An associative mechanism entails the removal of the ligand from the coordination sphere and attack by nucleophiles
and detectable intermediates. In addition, the formation of formate, i.e., the rate determining step (RDS) and the adsorption
of CO, CO2 , H2 , and H2 O on the catalyst surface are important aspects of this reaction (Chen et al., 2020). Kim et al. (2012)
discussed the effect of reducibility for RWGS reaction using Pt/Al2 O3 and Pt/TiO2 catalysts using a fixed bed reactor. The
findings were consistent with the redox surface mechanism. The X-ray photoelectron spectroscopy (XPS) analysis was
used to confirm the RWGS reaction, which took place at the Pt sites on the catalyst surface via oxidation and reduction
mechanisms. In Pt/TiO2 , a new active site was located, which entailed a larger conversion of CO2 , and a stronger metal-
support interaction. Goguet et al. (2006) applied the TAP technique on a 2% Pt/CeO2 catalyst with an associative reaction
mechanism for the RWGS reaction. Results revealed a small yield of CO when CO2 has pulsed alone over the catalyst, in
comparison to a larger yield of CO when both, CO2 and H2 were pulsed together. Jiang et al. (2022a) investigated CO2
hydrogenation with a series of promoters, such as La, Zr, Cr, Ca, Co, and Cd on ceria nanorods and studied the associative
mechanism. The results showed a linear dependency of oxygen vacancies and catalytic activity, especially with Zr, which
showed a more facile formation of oxygen vacancies. Additionally, Au-based catalysts supported on Al2 O3 and TiO2 for
RWGS reaction were studied via associative mechanisms. These reactions were characterized by steady-state and transient
operando diffuse reflectance infrared Fourier-transform spectroscopy (DRIFTS) studies (Bobadilla et al., 2018). Formate and
hydroxy carbonyl intermediates were created using Au/Al2 O3 and Au/TiO2 , and their subsequent decomposition into CO
and H2 O was attributed to the existence of O-vacancies and surface hydroxyls (Bobadilla et al., 2018). Ziemba et al. (2022)
proposed a reaction mechanism of the RWGS reaction over Au/ceria catalysts and showed the catalyst dynamics with
reaction intermediates via operando-transient spectroscopy and density functional theory (DFT) analysis. Fig. 2(c) shows
an overview of the associative mechanism with five steps: (1) reduction of ceria surface, (2) O-vacancy, which leads to
adsorption of CO2 and carbonate formation, (3) decomposition of carbonate and release of CO, (4) H2 with surface oxygen
to form H2 O (5) adsorption of CO2 . With insight into the specifics of the reduction of CO2 via formate and carbonate
production, transient DRIFTS demonstrated the separate processes of H2 dissociation on supported Au.
Yamano et al. (2023) investigated the application of an electric field for the enhancement of RWGS reaction highly
dispersed Ru/ZrTiO4 catalysts, which resulted in improved CO selectivity, suppressing CO hydrogenation into CH4 at the
4
Fig. 2. (a) Schematic diagram for CO2 conversion on Pt/Al2 O3 model catalyst. Carbon, hydrogen, and oxygen atoms are represented in gray, white
and black, respectively (Ferri et al., 2002), (b) Redox mechanism on xCuAl catalyst (Ai et al., 2022), and (c) The associative mechanism over Au/CeO2
catalyst. Oxygen, carbon, and hydrogen are represented in red, brown, and white, respectively (Ziemba et al., 2022). (For interpretation of the
references to color in this figure legend, the reader is referred to the web version of this article.)
5
Fig. 3. (a) Associative reaction at low-temperature RWGS reaction at dispersed Ru catalysts with and without electric field (Yamano et al., 2023)
and (b) Suggested reaction mechanism over Pt/CeO2 .
Ru surface by the enhanced hydrogen migration, as demonstrated in Fig. 3(a). The reaction was carried out through an
associative mechanism with the presence of oxygen vacancies for CO2 activation at low temperatures with the applied
electric field. Zhang et al. (2020b) prepared a Pt/γ -Mo2 N catalyst that exhibited excellent catalytic activity/stability for
RWGS reaction. MoO3 species were discovered on the surface of the catalyst, which was easily reduced to Mo oxide
at ambient temperature and created active oxygen vacancies to dissociate H2 O molecules. Goguet et al. (2004) studied
the reactivity of surface species at Pt/CeO2 catalyst via an association mechanism, as shown in Fig. 3(b). A DRIFT cell
reactor was used for spectroscopic measurements. The coverage of 12 C and 13 C were monitored simultaneously, and results
indicated that DRIFTS was not the main reaction under experimental conditions.
4. Noble metal catalysts for reverse water-gas shift reactions
Noble metals, i.e., platinum (Pt), palladium (Pd), ruthenium (Ru), silver (Ag), iridium (Ir), and gold (Au) are the most
frequently used metal-based catalysts, which have shown outstanding performances in RWGS reactions with promising
corrosion resistance and strong activity in H2 dispersions (Liu et al., 2019; Su et al., 2017; Chen et al., 2022a). The Ru
and Rh have demonstrated excellent catalytic activities in CO2 methanation via RWGS intermediates. The synthesis of CO
depends on promoters, catalytic supports, and particle size/distribution (Su et al., 2017).
The Pt-based catalysts are easily dispersed on reducible metal oxides because of the presence of abundant surface
oxygen vacancies and provide a pathway effective and conducive to the adsorption and activation of CO2 (Chen et al., 2016;
6
Fig. 4. An overview of the evolution of Pt1 /TiO2 during the activated redox cycle (Chen et al., 2021b).
Wang et al., 2016). However, enhanced CO2 conversion rates and large CO selectivity at elevated reaction temperatures
in RWGS, are the key challenge to the Pt-based catalysts. Hence, Zhao et al. (2021) studied the dispersion of Pt particles
toward high CO selectivity and inhibition of CH4 formations. The Pt/CeO2 catalysts were produced via the hydrothermal
technique and surface pre-reduction method and the effect of Pt size distribution was investigated. The CO2 conversions
were increased significantly with the addition of Pt on CeO2 at elevated temperatures while the maximum selectivity
for CO of more than 98% was reported over the temperature of 200-450 ◦ C. Atomic dispersion of large Pt species
demonstrated strong adsorption toward CO and the formation of methane was attributed to more CO hydrogenation with
Pt/CeO2 catalysts. Overall, 5Pt/CeO2 -IMP-350 (4.8 wt% Pt loading, 21.7 wt% Pt-dispersion) achieved up to around 45% CO2
conversions at 450 ◦ C and the CO selectivity declined from 98 to 32% as the reaction temperature raised to 450 ◦ C. Liu et al.
(2022b) utilized the varied amounts of Re with Pt-Re/SiO2 catalysts and investigated for RWGS reaction. Characterization
analysis verified the presence of partial coverage and electronic interaction with the oxophilic ReO x (0 ≤ x ≤ 3.5), leading
to 3.9 times more turnover frequency (2.30 s−1 ) than that on Pt/SiO2 under differential conditions. Overall, Pt and oxophilic
ReOx facilitates H2 and CO2 activation, respectively, and Pt/ReOx interface with balanced hydrogenation and C–O cleavage,
resulting in synergistically improved RWGS reactions. Liang et al. (2017) studied K@Pt/mullite for RWGS reaction, which
showed a 7-times more turnover frequency (TOF) than Pt/mullite at 340 ◦ C. The H2 temperature-programmed reduction
(H2 -TPR) verified the stabilized and strong interaction between KOx and Pt and XPS analysis demonstrated the formate
decomposition route. At 550 ◦ C, the CO2 conversion was 30.9%, and the selectivity of CO fell significantly from 96.7 to
95.1% between 300 and 400 ◦ C. Chen et al. (2021b) investigated the stabilization and improved dynamic reaction based on
Pt/TiO2 for RWGS reaction via redox mechanisms. The reduction process, controlled cleavage of Pt–O bonds, and excellent
mobilizing of Pt with stability for the re-dispersion were discussed, as shown in Fig. 4. The re-oxidation/re-dispersion of
Pt into Pt1 was based on less O-coordinated entities, more accessible, and more active towards RWGS reaction. Similar
research was done by Xing et al. (2021), by using the impregnation leaching process to synthesize the single atomic Pt
on SrTiO3 and found a 45% CO2 conversion rate, 100% CO selectivity, and a TOF of 0.643 s−1 at 500 ◦ C. DFT calculations
were performed that revealed a formate route with single Pt atoms with a significantly reduced reaction barrier for Pt
clusters and single Pt atoms from 1.54 to 1.29 eV, respectively.
In addition, Pt nanoparticles are considered sandwiched promoters for the enhancement of the RWGS reaction. Chen
et al. (2023) discussed the light-induced switching reaction mechanism with atomically dispersed Co decorated Pt@UiO-
66-NH2 for RWGS, attributing thermocatalysis, which excited electron transfer of UiO-66-NH2 Pt nanoparticles and Co
sites and efficiently catalyzing the reaction elementary steps. In a similar work, core–shell catalyst Pt/SAPO-34@UIO-
66 bicomponent composites containing silicoaluminophosphate (SAPO) were reported to boost the yield of CO, and the
synergistic impact of UIO-66 for CO2 conversions was examined (Wu et al., 2021). The results showed a significantly
improved CO selectivity and yield of 89.2 and 24.26%, respectively. Octahedral core–shell bimetallic catalysts based on
7
Zr-based Metal–organic frameworks (MOFs) catalysts Pt, Pd (nanoparticles (NPs) and nanocrystals (NCs))@UIO-67 were
investigated by Zhang et al. (2020a) for RWGS reaction. The experimental results demonstrated a greater 1.44-fold activity
over UIO-67 for Pt–Pd (NCs) than Pt–Pd (NPs) under similar reaction conditions, attributed to more active sites. At the
temperature of 400 ◦ C and 20 bar pressure, the H2 /CO2 ratio (5:1) showed a maximum CO2 conversion of 26.88% and
selectivity of around 62.51% with Pt–Pd (NCs) over UIO-67. In another study, Pt–Ni@UiO-67 experimented with Pt–Ni
alloy nanobead chains similar to the core in UiO-67 and reported an enhanced CO2 conversion with a 13.2 nm-UiO-67
membrane (Jiang et al., 2022b).
The addition of Pd is also investigated with a focus on the superior activity and selectivity for the performance of
RWGS reaction. For instance, (Yan et al., 2022) proposed a novel nano-catalyst based on the enriched oxygen vacancy CoPd
hybrid cluster-anchored Pd nanoparticles on cobalt oxide support base (CP-CoOx VPd) assisted with a galvanic replacement
reaction-assisted wet chemical reduction method. The modified catalyst showed a CO production yield of about 3414 µmol
g−1 with a CO selectivity of 99% in the presence of CO2 /H2 = 1/3 at 523 K. Both surface-anchored CoO x VPd clusters and
Pd domain enhanced CO2 adsorption/activation and H2 dissociation, respectively. Ma et al. (2020) discussed Pd as single-
atom catalysts (SACs) with 5 wt% loading under a reducing atmosphere and showed a high CO2 conversion to CO (>98%)
and thermal stability of 400 ◦ C. Moreover, Pd was dispersed on the surface of TiO2 during the RWGS reaction at 400 ◦ C by
mixing the pre-catalyst (Pd/TiO2 ) with new TiO2 Szanyi et al. (2020). The improvement in thermal stability and efficient
CO2 conversion was caused by the existence of oxygen vacancies and the large active surface area. Li et al. (2021) reported
Zr-based MOF catalysts for CO2 hydrogenation by using the surface coating approach and Pd/UiO-66, Pd/PtNPs/UiO-66, and
Pd/PtNCs/UiO-66 were prepared (encapsulation and etching). Pd/PtNCs/UiO-66 demonstrated the highest CO2 conversion
of 19.6% and CO selectivity of 72.3% among all other catalyst modifications, which were attributed to synergism effect
and more active sites at 400 ◦ C, 20 bar, CO2 /H2 of 3:1. In another novel study, hydrogenated bronze nanowires were
decorated with Pd (Pd/Hy WO3−x ), and then Cu atoms were conformably coated to synthesize Cu/Pd/Hy WO3−x for the
enhancement of photocatalytic RWGS reaction (Li et al., 2019). The experimental work revealed the synergistic synthesis
of surface carboxyl species and an up to 300%–500% increase in the rate of CO generation. The addition of the metal
anchoring method was considered as an alternative surface modifier to metal oxide (MOx ) nanomaterials for catalytic
applications (Li et al., 2019).
The Rh-based catalysts have exhibited remarkable accomplishment in the hydrogenation of hydrogenation, especially
RWGS reaction to obtain high selectivity of CO. The Rh NPs with modification have been studied to get maximum CO2
conversions by tuning their properties for effective loading. Tang et al. (2019) discussed Rh as the SAC on the surface of
TiO2 under various sets of operating conditions (i.e., O2 calcination, H2 reduction, CO adsorption) for RWGS reaction. The
detailed experimentation explained the switching of local coordination from inactive to active structures in single-atom
catalysts. Moreover, a wide range of support materials like CeO2 , MgO, Al2 O3 , SiO2 , zeolites, ZrO2 , Fe2 O3 , transition metal
carbides, and MOFs were studied with a combination of noble metal NPs for the high metal dispersion, optimum particle
size distribution and improved catalytic performance with maximum CO selectivity (Mathew et al., 2021). In addition,
unique metal–metal oxide structures have been linked to increased H2 dissociation activity and CO2 conversions that
are close to equilibrium with thermal stability above 500 ◦ C. Heyl et al. (2016) investigated the effect of Ni-Rh/Al2 O3
and K-Rh/Al2 O3 catalyst dispersion on the performance in CO generation at low temperatures between 250 and 350 ◦ C.
Operando DRIFTS and spectroscopic studies revealed that CO2 was adsorbed onto K-support and formed carbonate. A
chain reaction intermediate for the generation of CO was created when the activated H2 was coupled with the carbonate
of Rh to produce CO along with additional highly reactive formate species (F2 )., as displayed in Fig. 5.
The Au NPs have been reported for CO oxidation and WGSR because of excellent hydrogenation capability with no
electron transportation observed with the outer orbital of Au. The dispersion attributes of Au were applied on the surfaces
of Al2 O3 (Chen et al., 2016) and CeO2 (Wang et al., 2013) and the resulting support catalyst showed a high CO selectivity
of up to 99%. Rabee et al. (2023) performed an analysis of low Au loading with support of TiO2 and ZrO2 and characterized
them using scanning transmission electron microscopy (STEM), Brunauer-Emmett-Teller (BET), XPS, and in-situ DRIFTS.
Au/TiO2 catalytic activity was found to be 10-fold more than Au/ZrO2 because of interfacial Au–Ov –Ti3+ sites. Over
Au/ZrO2 , the formate mechanism predominates, whereas, over Au/TiO2 , the reaction was carried out via the production of
hydroxy carbonyl intermediates, as demonstrated in Fig. 6 that also shows the oxygen vacancies. Recently, Xu et al. (2017)
explored the interaction between AuNPs and UIO-67 for the enhanced performance of RWGS reaction in a fixed-bed flow
reactor by monodispersed Au NPs (Au NPs) on the surface Zr(IV)-based MOF UIO-67 support. A high CO2 conversion of 35%
was observed at 2.40 wt% Au@UIO-67 and steadily increased at the elevated reaction temperature. Lu et al. (2019) reported
photo-thermal RGWS with a high conversion rate of 40%, selectivity of CO of about 99%, and stable activity with Au/CeO2 ,
exhibiting H2 dissociation under photothermal conditions. Zhao et al. (2018) developed a novel microporous MOF based
on the encapsulation of core–shell with Au@Pd, followed by monodisperse of Pt nanospheres and functionalized on the
surface of Co complex, i.e., Pt/Au@Pd@1Co for RWGS reaction. At 8 wt% Pt addition, the experimental results showed CO2
conversion of 18.2% and CO selectivity of 96.1% at 400 ◦ C. The strategies, i.e., localized surface plasmon resonance (LSPR)
or plasmonic enhancement techniques, as presented in Fig. 7, and the deposition of oxygen storage/release species (MoOx
phase), were employed to minimize the problems (Su et al., 2017).
In general, the utilization of noble metallic catalysts has shown promising results toward CO2 hydrogenation to CO.
Still, the high costs and high activity in the CO2 methanation make their applications limited for their significant use in
large industrial-scale CO2 conversion processes; hence, promoters are still required to compensate the shortcomings of
these precious metal catalysts. Table 1 summarizes the involvement of noble metal-based catalysts to CO synthesis.
8
Fig. 5. A formate-based mechanism over Rh/Al2 O3 catalysts (Heyl et al., 2016).
Fig. 6. (a) Reaction mechanisms over (a) Au/ZrO2 and (b) Au/TiO2 catalysts (Rabee et al., 2023).
5. Noble metal-based catalysts: Types and potential
The high catalytic activity of Ag and Au has been reported in many experimental studies for the synthesis of methanol.
For instance, loading Ag on Ni can minimize methanation reaction during RWGS. The direct contact between the highly
dispersed Ag and Ni showed a surface modification that would reduce the accessible surface Ni sites and electron
migrations from Ni to Ag. Ni-0.3 Ag/SiO2 showed a 100% CO selectivity at 400 ◦ C with gas hourly space velocity (GHSV)
of more than 300 L g−1 h−1 (Zhang et al., 2023). Alotaibi et al. (2021) synthesized zeolite-based Ag–Cu catalysts at varied
ratios 1:9, 2:8, 4:6, and 1:1 wt% ratios. BET surface areas, pore sizes, and pore volumes showed no significant changes
upon the various loading Ag–Cu weight ratio. The manifestation of metal–metal chemical interaction with Ag, in addition
to the zeolite-based Ag–Cu bimetallic catalysts, was revealed by X-ray diffraction (XRD) and scanning electron microscopy
1
(SEM) analysis. 4Ag6CuZ exhibited a maximum methanol synthesis rate (72 g kg− (cat) h
−1
) at reaction temperature of
◦
230 C and pressure of 30 bars. In another study, the effect of Ag addition was investigated with Ag/CuO/ZrO2 (ACZ)
catalysts by using the incipient wet impregnation method (Tada and Satokawa, 2018). According to the H2 -TPR profiles,
Ag helped Cu particles sinter, and selectivity was based on a monotonic rise with increasing Ag loading. At 5 wt% Ag
loading, Ag/ZrO2 catalyst with Cu 0 wt.% loading displayed maximum methanol selectivity of 70%, which was more than
that of the 5 wt% Ag loading ACZ catalyst with 65% methanol selectivity, indicating new active sites (Tada and Satokawa,
9
Fig. 7. A mechanism for plasmonic enhancement of RGWS reaction on Au/TiO2 catalyst (Upadhye et al., 2015).
Table 1
Summary of the involvement of noble metal-based catalysts to CO synthesis.
Catalyst composition (wt.%) Temperature, pressure (◦ C, Bar) H2 :CO2 CO2 conversion (%) CO selectivity (%) Ref.
1 wt% Pt/CeO2 (500, 1) 1 30 99 Chen et al. (2016)
Pt/CeO2 (4.8-1) (450, 1) 3 ∼46 >98 Zhao et al. (2021)
Pt/K-mullite (2-5) (550, 1) 1 30.9 99.2 Liang et al. (2017)
Pd/SrTiO3 (0.17-1) (500, 1) 1 45 100 Xing et al. (2021)
Pt/SAPO-34@UIO-66 (400, 30) 5 27 89.2 Wu et al. (2021)
Pt–PdNCs@UIO-67 (400, 20) 3 17.91 81.02 Zhang et al. (2020a)
Ni-Pd-Ir/CeZrO2 (10-2-0.1) (750, 1) 1 52.4 98 Ajakaiye Jensen et al. (2021)
Rh/FeCeO2 (1-20) (600, 1) 1 ∼39 100 Kim et al. (2022a)
Au/CeO2 (0.9-1) (400, 1) 4 40 100 Lu et al. (2019)
Ag/Al2 O3 (5-95) (900, 1) 3 60 100 Choi et al. (2017a)
Pt/TiO2 (1-5) (400, 1) 1 21 95 Chen et al. (2017)
Pt-K/3Al2 O3 .2SiO2 (550, 1) 1 30.9 99.2 Liang et al. (2017)
Pt/La-ZrO2 (1-10) (150. -) 1 40.6 99.2 Oshima et al. (2014)
Pt-Co/MCF-17 (50-5) (300, 5.5) 3 5 – Alayoglu et al. (2011)
K-Pt/L (500, 1) 1 27.4 100 Yang et al. (2017)
0.3 wt% Pt/L (500, 1) 1 13.1 97 Yang et al. (2017)
Rh/Al2 O3 (800, 1) 4 80 – Büchel et al. (2014)
Rh/Al2 O3 -K (525, 1) 4 ∼52 – Büchel et al. (2014)
Rh/SiO2 (1-1) (200, 50) 3 0.52 88.1 Kusama et al. (2001)
Rh-Fe/TiO2 (2–2.5) (270, 120) 1 9.16 28.4 Gogate and Davis (2010)
2018). The connection interface between ZrO2 and Cu-Ag alloy reduce the production of CO and increased the selectivity
for methanol. Bharath et al. (2021) utilized photoelectrochemical (PEC) technology by Ag NPs modified on the surface
of TiO2 /reduced graphene oxide (rGO) photo-electrocatalyst. The Ag/TiO2 NPs were found to develop on the transparent
layers of folded rGO sheets using high-resolution transmission electron microscopy (HR-TEM) analysis, which reduced the
aggregation of TiO2 NPs, enhancing more CO2 conversions. Ag-TiO2 /rGO demonstrated a high methanol yield of 85 µmol
L−1 cm−2 , an increased specific surface area of 144 m2 g−1 , a photocurrent response of 23.5 mA cm−2 at 50 mV s−1 , and
a decreased electrode resistance value of 125 . Furthermore, Ren -UIO-67 with Ag nanocubes with plasmonic surface
energy showed the formation of photoactive centers, favoring an enhanced photocatalytic activity, conversion by 7-fold
and long-term catalytic stability of 48 h (Choi et al., 2017b).
In addition, the addition of Au NPs was reported bimetallic catalytic system of CuO/CeO2 catalysts (Au loading = 0.5,
1, 2 wt%) (Wang et al., 2021b). It was reported that Au NPs enhance the formation of Ov and promote the concentration
of Ce3+ /(Ce4+ + Ce3+ ). At 240 ◦ C and 30 bar. A 1 wt% Au-CuO/CeO2 achieved methanol selectivity of 29.6%. Multi-step
10
hydrogenation of bicarbonate to formate and methoxy, followed by the synthesis of methanol, was discovered by in situ
DRIFT calculations (Wang et al., 2021b). Additionally, the influence of ZnO particle size (22–103 nm) was investigated
with added Au NPs, and the results demonstrated a volcano-shaped pattern with the activity for methanol synthesis.
This was accomplished by increasing ZnO particle size while maintaining constant Au-loading (Chen et al., 2021a). This
was attributable to better electronic alterations of the Au interface perimeter sites, which increased the charge transfer
to the Au sites and caused more Ov defects in the ZnO unit cells, as shown by electron paramagnetic resonance (EPR)
spectroscopy. At 0.91 wt% Au-loading, the maximum rate of methanol (∼10.1 µmolMeOH g− 1
(Au) s
−1
), and selectivity of
◦
50% were observed H2 /CO2 (3:1) at 240 C and 50 bar. The methanol selectivity was increased up to 80% with a ZnO
particle size of 100 nm (Chen et al., 2021a). Yang and Jiang (2021) designed MOF-supported single-site catalysts with
N-heterocyclic carbene (NHC) in which coinage metal hydrides were accommodated on an organic linker, enhancing
heterolytic dissociation of H2 via formate mechanisms.
Among all noble metal categories, Pd-based catalysts have shown excellent characteristics for methanol synthesis.
Cai et al. (2022) utilized Pd/In2 O3 catalyst by considering MIL-68(In) as precursors and reported improved performance
with the formation of the bimetallic (In–Pd) phase. This method was based on the involvement of TCPP(Pd) as a dopant
over MIL-68(In) and carried for migration of the Pd2+ , which uniformly dispersed Pd0 species during reduction processes.
At 295 ◦ C and pressure of 30 bars with different Pd loading contents, such as 0.35, 0.53, 0.7, and 1.0 wt%, Pd0.53 /In2 O3
demonstrated high CO2 conversion of 8% and selectivity of 81%, corresponding to space–time yield (STY) of methanol
1
of 81.1 gMeOH g− (Pd) h
−1
. The DFT calculations were performed, which exhibited strong metal-support bonding and an
abundance of oxygen vacancies. In another study, doping of transition metals on Pd-clusters was discussed with a
combination of DFT calculations and microkinetic analysis for methanol synthesis and exhibited towards the formate
pathway (Saputro et al., 2021). Among all of them, Pd6 Ni clusters displayed better TOF profiles than Cu (111) surface,
indicating a decrease in the activation energy. Lee et al. (2022) reported an atomic solid solution catalyst (Pd-ZnZrO2 )
that exhibited enhanced methanol production. All Pd-ZnZrO2 catalysts displayed a single reduction peak at temperature
(< 900 K) in H2 -TPR profiles up to 0.8 wt% Pd loading, which was attributed to Pd species uniformly dispersed in ZnZrO
x and supported by TEM images. All Pd-ZnZrOx catalysts marked maximum STY of methanol from 593 to 613 K, which
increased proportionally with Pd content up to 0.8%. In situ DRIFTS showed that Pd doping enhanced H2 dissociation via
the formation of HCOO∗ . In another study, Pd-In2 O3 interfacial active sites showed strong interaction via Pd and peptide
composite under thermal treatment (Rui et al., 2017). The TEM images exhibited uniform dispersion of Pd NPs exposed to
(111) facets with the mean particle size of value 3.6 nm. The presence of Ov enhanced CO2 adsorption and hydrogenation
with the superior performance of CO2 conversion of more than 20% and methanol selectivity of more than 70% at 300 ◦ C
and 50 bar (Rui et al., 2017).
Pt has been added to various supports for enhanced catalytic hydrogenation. To improve methanol synthesis, Pt-
clusters formed in situ from isolated Pt atoms in the support lattice were used. For instance, Izadpanah Ostad et al. (2021)
developed a photocatalytic CO2 reduction strategy with ZIF-8 decorated NPs of Pt, Cu, Au, and ZnO. The structural stability
of ZIF-8 was found upon the addition of NPs on the surface with acceptable crystallinity and prevented electron–hole
recombination during photocatalytic activity reduction from photoluminescence (PL) spectroscopy analysis. The semi-
hexagonal morphology (Pt and Au on ZIF-8) while semi-spherical shapes (Cu/ZIF-8) were displayed by TEM, illustrating
the spreading of NPs over the surface of ZIF-8. The large active areas were exhibited by ZnO/ZIF-8 and Pt/ZIF-8, which
marked appreciable methanol yield of 6700 and 5300 µmol g−1 after 1 h operation under ultraviolet/visible (UV/Vis.)
irradiation, respectively. Sun et al. (2021) reported The In2 O3 supported Pt clusters catalyst with DFT calculations, which
showed strong interactions promoted by the presence of surface-Ov , leading to C–O cleavage (crystal orbital Hamilton
population (COHP) method). Toyao et al. (2019) considered the incorporation of Pt nanoparticles on MoO2 /TiO2 as support,
which promoted selective hydrogenation of CO2 with a methanol yield of 73% under 150 ◦ C and 50 bars for 48 h. The
dispersion of MoO2 species over the TiO2 surface was examined by the TEM analysis. Table 2 summarizes the contribution
of the noble metal catalysts for the conversion of CO2 to methanol.
6. Noble metal catalysts: advantages and drawbacks
Due to the scarcity and expensive cost, noble metallic catalysts are not favored for experimental investigation. However,
in some cases, using noble metal catalysts provides more advantages than other metals. In RWGS reactions, Pt catalysts’
selectivity to CO in CO2 hydrogenation reactions can be enhanced by adding what is called a promoter, which acts as
the active site for the previously mentioned RWGS reaction (Bahmanpour et al., 2021) with very high selectivity to CO,
reaching a 100% (Kattel et al., 2016). Promising catalytic activity, and stability, coupled with the presence of oxygen
vacancies, are all highlighting features of Au-based catalysts in the activation of CO2 (Bobadilla et al., 2018). The Au-based
and Pd-based catalysts were reported for CO2 reduction/hydrogenation and the formation of formates (Bahmanpour et al.,
2021). The formates compounds could then decompose to yield CO and H2 O as products. Furthermore, and by utilizing Rh
catalysts, high conversion of CO2 to CH4 and CO can be achieved, which is excellent for modified methanol synthesis (MS)
and Fischer–Tropsch synthesis (FTS) (Zeng et al., 2021). The Au catalysts are used for local and decentralized conversion
and strong chemoselectivity (Keane et al., 2018). High activation and CO2 adsorption can also be produced by adjusting
the Au metal oxide interface (Hartadi et al., 2016).
Although noble metal catalysts provide a wide array of advantages, mainly the excellent catalytic activity at low
temperature operation and the stability, there are certain limitations. For instance, Au catalysts offer lowered reaction
11
Table 2
Noble-based catalysts’ contribution to the conversion of CO2 to methanol.
Catalyst type(wt.%) Temperature and pressure(◦ C, bar) H2 :CO2 CO2 conversion(%) Methanol selectivity(%) Ref.
Ag/CuO/ZrO2 (0.5-10) (230, 10) 3 1.4 64 Tada and Satokawa (2018)
5AZ (230, 10) 3 1.0 70 Tada and Satokawa (2018)
1 wt% Au–CuO/CeO2 (240, 30) 3 – 29.6 Wang et al. (2021b)
Au/ZnO (240, 50) 3 – 70 Chen et al. (2021a)
Pd/In2 O3 (0.53-1) (295, 30) 3 8 81 Cai et al. (2022)
Pd/In2 O3 (300, 50) 3 >20 >70 Rui et al. (2017)
Pt/MoO2 -TiO2 (3-30) (150, 60) – – 73 Toyao et al. (2019)
Pd (0.25)-Cu/SiO2 (250, 41) 3 6.7 30 Jiang et al. (2015)
Pd (0.25)-Cu-MCM-41 (250, 41) 3 6.2 23 Jiang et al. (2015)
Pd/CeO2 (220, 30) 3 1.7 70.1 Malik et al. (2018)
Pd/ZnO-3.93Al (250, 30) 3 14.2 7.3 Song et al. (2020)
5 wt% Pd/β -Ga2 O3 (250, 50) 3 17.33 51.62 Qu et al. (2014)
9 wt% In2 O3 /ZrO2 (300, 50) 4 – 100 Martin et al. (2016)
Ni-Ga (250, 1.01) 3 – 98.5 Sharafutdinov et al. (2014)
1Au/C4 ZA (1-4-1-1) (260, 60) 6 28 16.6 Pasupulety et al. (2015)
rates compared to other metals and are quite expensive. They are also unstable when used in pure form and need to be
conjugated with other elements before use. The Pt catalysts, in general, are also expensive and cannot be recycled easily
if deactivation happens (Chen et al., 2022b). They are highly sensitive to the particle size of CO2 hydrogenation. The Pd
catalysts are not preferred for RWGS reactions due to their selectivity towards CH4 . The size, structure, and composition
of Pt catalysts greatly influence catalytic activities. Finally, to overcome the kinetic constraints for CO2 conversion, Rh
catalysts are more expensive and necessitate high reaction temperatures (Wang et al., 2021a).
7. Advancement in catalytic hydrogenation
Due to the electronic excitation and thermal energy characteristics, photothermal catalysis has received a lot of
attention in recent years in a variety of industrial and commercial applications. It also promises to make a significant
contribution to the acquisition of catalytic surface temperatures. To increase catalytic reaction under photo-radiation and
induce charge transfer, photocatalysis, and thermocatalysis have been integrated into a hybrid technology (Jiang et al.,
2023b; Dong et al., 2023; Bafaqeer et al., 2023). Using CO2 hydrogenation in combination with photothermal catalysis
is a promising and developing strategy to address environmental issues. Dong et al. (2023) discussed the synthesis
of TiOx nanoparticles (oxygen vacancies by laser bombardment) and studied the effect of uniform Ru nanoparticles
on the TiOx (Ru-TiOx ) by photothermal reduction. In the same study by Dong et al. (2023), the synergistic effect
between photocatalysis and thermocatalysis of Ru-TiOx exhibited high activity, methane yield of 15.84 mmol g−1 h−1 ,
and selectivity of 99.99%. In addition, heterogeneous oxide-zeolite (OX-ZEO) bifunctional catalysts have shown promising
results following the nature of metal oxide and their selective modification for improved catalytic performance on CO2
hydrogenation (Zhang et al.). The selectivity towards methane is greatly influenced by the type/nature of the noble metal
catalyst. It was found that the use of bimetallic catalysts has a significant impact on the selectivity of CO2 hydrogenation.
For instance, when metal–metal oxides are utilized as catalysts, like in the case of K paired with Pt, a new active site
is produced. The reaction’s active site, Pt-KOx , has been discovered (Kattel et al., 2017). Overall, CO2 conversion appears
as a promising sustainable technology for producing fuels (Chakravarty and Mallick, 2022). With a focus on Pt, Pd, Rh,
and Au as preferred choices for various processes, including direct gas phase hydrogenation and modified methanol
synthesis (Sharma et al., 2022).
8. Conclusions and prospects
With the increase in CO2 emissions, efficient and sustainable technology is required. This review discussed the most
recent and significant developments in CO2 hydrogenation processes via noble metal catalysts. This work shows that
extensive efforts were invested in studying the catalytic CO2 hydrogenation to other products, such as CO, methanol, and
DME.
Noble metallic-based catalysts, including Pt, Pd, Rh, and Au, have been all investigated due to their excellent selectivity
and enhanced ability to convert CO2 into valuable chemicals. By producing Lewis acid–base complexes between O and
CO, Au catalysts, for example, can improve the CO and CO2 hydrogenation process. The Pd catalysts, on the other hand,
have been shown to be among the most efficient in producing methanol, whereas studies utilizing Pt catalysts have
demonstrated very high product selectivity.
Noble metal catalysts for catalytic CO2 hydrogenation have been the subject of extensive literature reviews and research
studies. However, there are several gaps that must be addressed to enhance the catalytic activity and selectivity. Novel
supports are to be designed to include the unique properties of noble metals, such as low reactivity, thermal stability,
oxygen vacancies, and basicity. Additionally, novel methods of catalyst preparation must be investigated to maximize
12
support interaction and catalyst activity. The mechanism route, reaction kinetics, and operating variables must be studied
in detail to devise the ideal catalyst preparation reaction. To distinguish between active sites, in situ characterization
methods, such as XRD, TEM, and X-ray absorption, should be used. Analytical techniques like XPS and DFT analysis are
then needed to identify the major surface species and to provide an understanding of the reaction mechanism of CO2
hydrogenation to value-added products.
The most notable challenge in the catalytic conversion of CO2 hydrogenation is the stability of the molecule itself,
which leads to low yields. To overcome the equilibrium limitation on product yield, thermodynamic features of CO2
hydrogenation should also be considered in addition to more research on the catalyst side. The challenges on the catalyst
side could be related to deactivation and or/poisoning as well as the cost for large scale applications. Hence, reaction
conditions optimization needs to be considered. Furthermore, a thorough analysis of the design and optimization of CO2
hydrogenation reactors is required. Thus, new reactors have been developed, such as perm-selective membrane reactors,
to remove water and thereby alter the thermodynamic equilibrium in favor of the desired product.
The development of affordable and environmentally friendly noble metal catalysts is crucial for the feasibility of the
hydrogenation process. The extraction and synthesis of these metals must be investigated to reduce the associated costs
and make them more easily available to researchers. To maximize overall performance in terms of operational and
financial factors, hybrid reactors with renewable energy resources integrated with both cyclic adsorption/regeneration
phases in the sorption-enhanced processes can be adjusted and improved. Instead of separate systems, future research
should concentrate on developing reactors that can mitigate environmental concerns while also being effective and
affordable.
CRediT authorship contribution statement
Muhammad Tawalbeh: Conceptualization, Project administration, Supervision, Investigation, Methodology, Data cu-
ration, Writing – original draft, Writing – review & editing. Rana Muhammad Nauman Javed: Investigation, Data
curation, Formal analysis, Writing – original draft, Writing – review & editing. Amani Al-Othman: Conceptualization,
Administration, Investigation, Methodology, Writing – original draft, Writing – review & editing. Fares Almomani:
Conceptualization, Methodology, Formal analysis, Writing – original draft, Writing – review & editing. Saniha Ajith:
Investigation, Data curation, Formal analysis, Writing – original draft, Writing – review & editing.
Declaration of competing interest
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.
Data availability
Data will be made available on request.
Acknowledgments
The authors would like to thank the University of Sharjah, United Arab Emirates for financial support via the
competitive research grant project number: 22020406230. The authors would like to acknowledge the open access funding
provided by the Qatar National Library.
References
Ai, X., Xie, H., Chen, S., Zhang, G., Xu, B., Zhou, G., 2022. Highly dispersed mesoporous Cu/γ -Al2O3 catalyst for RWGS reaction. Int. J. Hydrogen
Energy 47 (33), 14884–14895. http://dx.doi.org/10.1016/j.ijhydene.2022.03.002.
Ajakaiye Jensen, L.I., Blomberg, S., Hulteberg, C., 2021. Effect of Pd and Ir as promoters in the activity of Ni/CeZrO2 catalyst for the reverse water-gas
shift reaction. Catalysts 11 (9), http://dx.doi.org/10.3390/catal11091076.
Alami, A.H., Tawalbeh, M., Alasad, S., Ali, M., Alshamsi, M., Aljaghoub, H., 2021. Cultivation of nannochloropsis algae for simultaneous biomass
applications and carbon dioxide capture. Energy Sources, Part A Recover. Util. Environ. Eff. 1–12. http://dx.doi.org/10.1080/15567036.2021.1933267.
Alami, A.H., et al., 2020. Materials and logistics for carbon dioxide capture, storage and utilization. Sci. Total Environ. 717, 137221. http://dx.doi.org/
10.1016/j.scitotenv.2020.137221.
Alayoglu, S., et al., 2011. CO2 hydrogenation studies on co and CoPt bimetallic nanoparticles under reaction conditions using TEM, XPS and NEXAFS.
Top. Catal. 54 (13), 778. http://dx.doi.org/10.1007/s11244-011-9695-9.
Almomani, F., Al-Rababah, A., Tawalbeh, M., Al-Othman, A., 2023. A comprehensive review of hydrogen generation by water splitting using 2D
nanomaterials: Photo vs electro-catalysis. Fuel 332, 125905. http://dx.doi.org/10.1016/j.fuel.2022.125905.
Almomani, F., Bhosale, R., Khraisheh, M., Kumar, A., Tawalbeh, M., 2019. Photocatalytic conversion of CO2 and H2O to useful fuels by nanostructured
composite catalysis. Appl. Surf. Sci. 483, 363–372. http://dx.doi.org/10.1016/j.apsusc.2019.03.304.
Alotaibi, M.A., et al., 2021. Green methanol synthesis by catalytic CO2 hydrogenation, deciphering the role of metal–metal interaction. Sustain. Chem.
Pharm. 21, 100420. http://dx.doi.org/10.1016/j.scp.2021.100420.
Bafaqeer, A., Tahir, M., Amin, N.A.S., Al-Bastaki, N., Altowayti, W.A.H., Thabit, H.A., 2023. Performance analysis of externally reflected photoreactor
for CO2 conversion to methanol using f-C3N4/ZnV2O6 S-scheme photocatalyst. Environ. Technol. Innov. 30, 103032. http://dx.doi.org/10.1016/j.
eti.2023.103032.
13
Bahmanpour, A.M., Signorile, M., Kröcher, O., 2021. Recent progress in syngas production via catalytic CO2 hydrogenation reaction. Appl. Catal. B
Environ. 295, 120319. http://dx.doi.org/10.1016/j.apcatb.2021.120319.
Belekar, R.M., 2021. Suppression of coke formation during reverse water-gas shift reaction for CO2 conversion using highly active Ni/Al2O3-CeO2
catalyst material. Phys. Lett. A 395, 127206. http://dx.doi.org/10.1016/j.physleta.2021.127206.
Bharath, G., et al., 2021. Synthesis of TiO2/RGO with plasmonic Ag nanoparticles for highly efficient photoelectrocatalytic reduction of CO2 to methanol
toward the removal of an organic pollutant from the atmosphere. Environ. Pollut. 281, 116990. http://dx.doi.org/10.1016/j.envpol.2021.116990.
Bobadilla, L.F., Santos, J.L., Ivanova, S., Odriozola, J.A., Urakawa, A., 2018. Unravelling the role of oxygen vacancies in the mechanism of the reverse
water–gas shift reaction by operando DRIFTS and ultraviolet–Visible spectroscopy. ACS Catal. 8 (8), 7455–7467. http://dx.doi.org/10.1021/acscatal.
8b02121.
Büchel, R., Baiker, A., Pratsinis, S.E., 2014. Effect of Ba and K addition and controlled spatial deposition of Rh in Rh/Al2O3 catalysts for CO2
hydrogenation. Appl. Catal. A Gen. 477, 93–101. http://dx.doi.org/10.1016/j.apcata.2014.03.010.
Buckingham, J., Reina, T.R., Duyar, M.S., 2022. Recent advances in carbon dioxide capture for process intensification. Carbon Capture Sci. Technol. 2,
100031. http://dx.doi.org/10.1016/j.ccst.2022.100031.
Cai, Z., et al., 2022. Fabrication of Pd/In2o3 nanocatalysts derived from MIL-68(In) loaded with molecular metalloporphyrin (TCPP(Pd)) toward CO2
hydrogenation to methanol. ACS Catal. 12 (1), 709–723. http://dx.doi.org/10.1021/acscatal.1c03630.
Chakravarty, S., Mallick, N., 2022. Carbon dioxide mitigation and biodiesel production by a marine microalga under mixotrophic mode by using
transesterification by-product crude glycerol: A synergy of biofuels and waste valorization. Environ. Technol. Innov. 27, 102441. http://dx.doi.org/
10.1016/j.eti.2022.102441.
Channiwala, S.A., Pathak, S.K., sood, V., Singh, Y., Gupta, S., 2017. Application of DME 20 fuel in a gasoline passenger car to comply with euro IV
emission legislation. http://dx.doi.org/10.4271/2017-01-0872.
Chen, Y., Li, M., Li, Z., Liu, F., Song, G., Kawi, S., 2022a. Efficient syngas production via CO2 reforming and electroreduction reactions through catalyst
design. Energy Convers. Manag. 265, 115744. http://dx.doi.org/10.1016/j.enconman.2022.115744.
Chen, X., Su, X., Duan, H., Liang, B., Huang, Y., Zhang, T., 2017. Catalytic performance of the Pt/TiO2 catalysts in reverse water gas shift reaction:
Controlled product selectivity and a mechanism study. Catal. Today 281, 312–318.
Chen, J., Wang, Y., Wang, F., Li, Y., 2023. Photo-induced switching of CO2 hydrogenation pathway towards CH3OH production over Pt@UiO-66-NH2(Co).
Angew. Chemie Int. Ed. 62 (9), e202218115. http://dx.doi.org/10.1002/anie.202218115.
Chen, X., et al., 2016. Identification of relevant active sites and a mechanism study for reverse water gas shift reaction over Pt/CeO2 catalysts. J.
Energy Chem. 25 (6), 1051–1057.
Chen, X., et al., 2020. Recent advances in supported metal catalysts and oxide catalysts for the reverse water-gas shift reaction. Front. Chem. 8.
Chen, S., et al., 2021a. Controlling the O-vacancy formation and performance of Au/ZnO catalysts in CO2 reduction to methanol by the ZnO particle
size. ACS Catal. 11 (15), 9022–9033. http://dx.doi.org/10.1021/acscatal.1c01415.
Chen, L., et al., 2021b. Unlocking the catalytic potential of TiO2-supported Pt single atoms for the reverse water–gas shift reaction by altering their
chemical environment. JACS Au 1 (7), 977–986. http://dx.doi.org/10.1021/jacsau.1c00111.
Chen, L., et al., 2022b. Imidazolinium-functionalized complexes of cobalt and iron as catalysts for hydrosilylation reactions. ChemistrySelect 7 (33),
http://dx.doi.org/10.1002/slct.202202482.
Chishti, M.Z., Ullah, S., Ozturk, I., Usman, A., 2020. Examining the asymmetric effects of globalization and tourism on pollution emissions in South
Asia. Environ. Sci. Pollut. Res. 27 (22), 27721–27737. http://dx.doi.org/10.1007/s11356-020-09057-9.
Choi, S., et al., 2017a. Catalytic behavior of metal catalysts in high-temperature RWGS reaction: In-situ FT-IR experiments and first-principles
calculations. Sci. Rep. 7 (1), 41207. http://dx.doi.org/10.1038/srep41207.
Choi, K.M., et al., 2017b. Plasmon-enhanced photocatalytic CO2 conversion within metal–organic frameworks under visible light. J. Am. Chem. Soc.
139 (1), 356–362. http://dx.doi.org/10.1021/jacs.6b11027.
Dai, B., et al., 2022. Hybrid CO2 air source heat pump system integrating with vapor injection and mechanical subcooling technology for space
heating of global application: Life cycle techno-energy-enviro-economics assessment. Energy Convers. Manag. 271, 116324. http://dx.doi.org/10.
1016/j.enconman.2022.116324.
Dat Vo, N., Oh, M., Lee, C.-H., 2022. Design guideline for CO2 to methanol conversion process supported by generic model of various bed reactors.
Energy Convers. Manag. 269, 116079. http://dx.doi.org/10.1016/j.enconman.2022.116079.
De, S., Dokania, A., Ramirez, A., Gascon, J., 2020. Advances in the design of heterogeneous catalysts and thermocatalytic processes for CO2 utilization.
ACS Catal. 10 (23), 14147–14185.
Dong, T., et al., 2023. Ru decorated TiOx nanoparticles via laser bombardment for photothermal co-catalytic CO2 hydrogenation to methane with
high selectivity. Appl. Catal. B Environ. 326, 122176. http://dx.doi.org/10.1016/j.apcatb.2022.122176.
Dostagir, N.H.M., Fukuoka, A., Shrotri, A., 2023. Redox behavior of In-O-Ti interface for selective hydrogenation of CO2 to CO in doped In-TiO2 catalyst.
ChemCatChem 15 (3), e202201348. http://dx.doi.org/10.1002/cctc.202201348.
Du, C., Wang, X., Chen, W., Feng, S., Wen, J., Wu, Y.A., 2020. CO2 transformation to multicarbon products by photocatalysis and electrocatalysis.
Mater. Today Adv. 6, 100071.
Faisal Elmobarak, W., Almomani, F., Tawalbeh, M., Al-Othman, A., Martis, R., Rasool, K., 2023. Current status of CO2 capture with ionic liquids:
Development and progress. Fuel 344, 128102. http://dx.doi.org/10.1016/j.fuel.2023.128102.
Fan, W.K., Tahir, M., 2022. Recent advances on cobalt metal organic frameworks (MOFs) for photocatalytic CO2 reduction to renewable energy and
fuels: A review on current progress and future directions. Energy Convers. Manag. 253, 115180. http://dx.doi.org/10.1016/j.enconman.2021.115180.
Fennell, P.S., Davis, S.J., Mohammed, A., 2021. Decarbonizing cement production. Joule 5 (6), 1305–1311. http://dx.doi.org/10.1016/j.joule.2021.04.011.
Ferri, D., Bürgi, T., Baiker, A., 2002. Probing boundary sites on a Pt/Al2O3 model catalyst by CO2 hydrogenation and in situ ATR-IR spectroscopy of
catalytic solid–liquid interfaces. Phys. Chem. Chem. Phys. 4 (12), 2667–2672. http://dx.doi.org/10.1039/B111498K.
Fu, L., et al., 2022. Research progress on CO2 capture and utilization technology. J. CO2 Util. 66, 102260. http://dx.doi.org/10.1016/j.jcou.2022.102260.
Gao, P., Zhang, L., Li, S., Zhou, Z., Sun, Y., 2020. Novel heterogeneous catalysts for CO 2 hydrogenation to liquid fuels. ACS Cent. Sci. 6 (10), 1657–1670.
http://dx.doi.org/10.1021/acscentsci.0c00976.
Gogate, M.R., Davis, R.J., 2010. Comparative study of CO and CO2 hydrogenation over supported Rh–Fe catalysts. Catal. Commun. 11 (10), 901–906.
http://dx.doi.org/10.1016/j.catcom.2010.03.020.
Goguet, A., Meunier, F.C., Tibiletti, D., Breen, J.P., Burch, R., 2004. Spectrokinetic investigation of reverse water-gas-shift reaction intermediates over
a Pt/CeO2 catalyst. J. Phys. Chem. B 108 (52), 20240–20246. http://dx.doi.org/10.1021/jp047242w.
Goguet, A., Shekhtman, S.O., Burch, R., Hardacre, C., Meunier, F.C., Yablonsky, G.S., 2006. Pulse-response TAP studies of the reverse water–gas shift
reaction over a Pt/CeO2 catalyst. J. Catal. 237 (1), 102–110. http://dx.doi.org/10.1016/j.jcat.2005.10.020.
González-Gómez, P.A., Laporte-Azcué, M., Fernández-Torrijos, M., Santana, D., 2022. Hybrid storage solution steam-accumulator combined to concrete-
block to save energy during startups of combined cycles. Energy Convers. Manag. 253, 115168. http://dx.doi.org/10.1016/j.enconman.2021.
115168.
Guo, L., Sun, J., Ge, Q., Tsubaki, N., 2018. Recent advances in direct catalytic hydrogenation of carbon dioxide to valuable C 2+ hydrocarbons. J. Mater.
Chem. A 6 (46), 23244–23262. http://dx.doi.org/10.1039/C8TA05377D.
14
Gurbanov, S., Mikayilov, J.I., Mukhtarov, S., Yagubov, S., 2023. Forecasting 2030 CO2 reduction targets for Russia as a major emitter using different
estimation scenarios. J. Appl. Econ. 26 (1), 2146861. http://dx.doi.org/10.1080/15140326.2022.2146861.
Hartadi, Y., Widmann, D., Behm, R.J., 2016. Methanol formation by CO2 hydrogenation on Au/ZnO catalysts – effect of total pressure and influence
of CO on the reaction characteristics. J. Catal. 333, 238–250. http://dx.doi.org/10.1016/j.jcat.2015.11.002.
Heyl, D., Rodemerck, U., Bentrup, U., 2016. Mechanistic study of low-temperature CO2 hydrogenation over modified Rh/Al2O3 catalysts. ACS Catal.
6 (9), 6275–6284. http://dx.doi.org/10.1021/acscatal.6b01295.
Hilaire, S., Wang, X., Luo, T., Gorte, R.J., Wagner, J., 2001. A comparative study of water-gas-shift reaction over ceria supported metallic catalysts.
Appl. Catal. A Gen. 215 (1), 271–278. http://dx.doi.org/10.1016/S0926-860X(01)00535-X.
Izadpanah Ostad, M., Niknam Shahrak, M., Galli, F., 2021. Photocatalytic carbon dioxide reduction to methanol catalyzed by ZnO, Pt, Au, and Cu
nanoparticles decorated zeolitic imidazolate framework-8. J. CO2 Util. 43, 101373. http://dx.doi.org/10.1016/j.jcou.2020.101373.
Jiang, F., Jiang, F., Wang, S., Xu, Y., Liu, B., Liu, X., 2022a. Catalytic activity for CO2 hydrogenation is linearly dependent on generated oxygen vacancies
over CeO2-supported Pd catalysts. ChemCatChem 14 (16), e202200422. http://dx.doi.org/10.1002/cctc.202200422.
Jiang, X., Koizumi, N., Guo, X., Song, C., 2015. Bimetallic Pd–Cu catalysts for selective CO2 hydrogenation to methanol. Appl. Catal. B Environ. 170–171,
173–185. http://dx.doi.org/10.1016/j.apcatb.2015.01.010.
Jiang, D., et al., 2022b. Pt–Ni alloy nanobead chains catalysts embedded in UiO-67 membrane for enhanced CO2 conversion to CO. Mater. Today
Energy 28, 101051. http://dx.doi.org/10.1016/j.mtener.2022.101051.
Jiang, Y., et al., 2023a. Energy-effective and low-cost carbon capture from point-sources enabled by water-lean solvents. J. Clean. Prod. 388, 135696.
http://dx.doi.org/10.1016/j.jclepro.2022.135696.
Jiang, Y., et al., 2023b. Recent advances in thermocatalytic hydrogenation of carbon dioxide to light olefins and liquid fuels via modified
Fischer–Tropsch pathway. J. CO2 Util. 67, 102321. http://dx.doi.org/10.1016/j.jcou.2022.102321.
Jing, T., et al., 2018. Fabrication of a robust lanthanide metal–organic framework as a multifunctional material for Fe(III) detection, CO2 capture, and
utilization. Cryst. Growth Des. 18 (5), 2956–2963. http://dx.doi.org/10.1021/acs.cgd.8b00068.
Junaidi, N.F.D., et al., 2021. Recent development of graphene oxide-based membranes for oil–water separation: A review. Sep. Purif. Technol. 258,
118000.
Kattel, S., Liu, P., Chen, J.G., 2017. Tuning selectivity of CO 2 hydrogenation reactions at the metal/oxide interface. J. Am. Chem. Soc. 139 (29),
9739–9754. http://dx.doi.org/10.1021/jacs.7b05362.
Kattel, S., Yan, B., Chen, J.G., Liu, P., 2016. CO2 hydrogenation on Pt, Pt/SiO2 and Pt/TiO2: Importance of synergy between Pt and oxide support. J.
Catal. 343, 115–126. http://dx.doi.org/10.1016/j.jcat.2015.12.019.
Keane, M.A., Li, M., Collado, L., Cárdenas-Lizana, F., 2018. Overcoming the limitations of gold catalysts in hydrogenation: enhanced activity with full
hydrogen utilization. React. Kinet. Mech. Catal. 125 (1), 25–36. http://dx.doi.org/10.1007/s11144-018-1417-x.
Kim, S.S., Lee, H.H., Hong, S.C., 2012. A study on the effect of support’s reducibility on the reverse water-gas shift reaction over Pt catalysts. Appl.
Catal. A Gen. 423–424, 100–107. http://dx.doi.org/10.1016/j.apcata.2012.02.021.
Kim, G., et al., 2022a. Gas-permeable iron-doped ceria shell on rh nanoparticles with high activity and durability. JACS Au http://dx.doi.org/10.1021/
jacsau.2c00035.
Kim, S., et al., 2022b. Perspectives of oxy-coal power plants equipped with CO2 capture, utilization, and storage in terms of energy, economic, and
environmental impacts. Energy Convers. Manag. 273, 116361. http://dx.doi.org/10.1016/j.enconman.2022.116361.
Kusama, H., Bando, K.K., Okabe, K., Arakawa, H., 2001. CO2 hydrogenation reactivity and structure of Rh/SiO2 catalysts prepared from acetate, chloride
and nitrate precursors. Appl. Catal. A Gen. 205 (1), 285–294. http://dx.doi.org/10.1016/S0926-860X(00)00576-7.
Lee, K., et al., 2022. Atomic Pd-promoted ZnZrOx solid solution catalyst for CO2 hydrogenation to methanol. Appl. Catal. B Environ. 304, 120994.
http://dx.doi.org/10.1016/j.apcatb.2021.120994.
Li, W., et al., 2018. A short review of recent advances in CO2 hydrogenation to hydrocarbons over heterogeneous catalysts. RSC Adv. 8 (14), 7651–7669.
http://dx.doi.org/10.1039/C7RA13546G.
Li, Y.F., et al., 2019. Cu atoms on nanowire Pd/HyWO3–x bronzes enhance the solar reverse water gas shift reaction. J. Am. Chem. Soc. 141 (38),
14991–14996. http://dx.doi.org/10.1021/jacs.9b08030.
Li, L., et al., 2021. Etching of cubic Pd@Pt in UiO-66 to obtain nanocages for enhancing CO2 hydrogenation. Mater. Today Energy 19, 100585.
http://dx.doi.org/10.1016/j.mtener.2020.100585.
Lian, S., Song, C., Liu, Q., Duan, E., Ren, H., Kitamura, Y., 2021. Recent advances in ionic liquids-based hybrid processes for CO2 capture and utilization.
J. Environ. Sci. 99, 281–295. http://dx.doi.org/10.1016/j.jes.2020.06.034.
Liang, B., et al., 2017. Promoting role of potassium in the reverse water gas shift reaction on Pt/mullite catalyst. Catal. Today 281, 319–326.
http://dx.doi.org/10.1016/j.cattod.2016.02.051.
Liu, M., Yi, Y., Wang, L., Guo, H., Bogaerts, A., 2019. Hydrogenation of carbon dioxide to value-added chemicals by heterogeneous catalysis and plasma
catalysis. Catalysts 9 (3), http://dx.doi.org/10.3390/catal9030275.
Liu, H.-X., et al., 2022a. Partially sintered copper - ceria as excellent catalyst for the high-temperature reverse water gas shift reaction. Nature
Commun. 13 (1), 867. http://dx.doi.org/10.1038/s41467-022-28476-5.
Liu, Y., et al., 2022b. Synergetic enhancement of activity and selectivity for reverse water gas shift reaction on Pt-Re/SiO2 catalysts. J. CO2 Util. 63,
102128. http://dx.doi.org/10.1016/j.jcou.2022.102128.
Lu, B., Quan, F., Sun, Z., Jia, F., Zhang, L., 2019. Photothermal reverse-water-gas-shift over Au/CeO2 with high yield and selectivity in CO2 conversion.
Catal. Commun. 129, 105724. http://dx.doi.org/10.1016/j.catcom.2019.105724.
Ma, Y., et al., 2020. High-density and thermally stable palladium single-atom catalysts for chemoselective hydrogenations. Angew. Chem. Int. Ed.
Engl. 59 (48), 21613–21619. http://dx.doi.org/10.1002/anie.202007707.
Malik, A.S., Zaman, S.F., Al-Zahrani, A.A., Daous, M.A., Driss, H., Petrov, L.A., 2018. Development of highly selective PdZn/CeO2 and Ca-doped PdZn/CeO2
catalysts for methanol synthesis from CO2 hydrogenation. Appl. Catal. A Gen. 560, 42–53. http://dx.doi.org/10.1016/j.apcata.2018.04.036.
Martin, O., et al., 2016. Indium oxide as a superior catalyst for methanol synthesis by CO2 hydrogenation. Angew. Chem. Int. Ed. 55 (21), 6261–6265.
http://dx.doi.org/10.1002/anie.201600943.
Mathew, T., Saju, S., Raveendran, S.N., 2021. Survey of heterogeneous catalysts for the CO2 reduction to CO via reverse water gas shift. Eng. Solut.
CO2 Convers. 281–316. http://dx.doi.org/10.1002/9783527346523.ch12.
Oshima, K., Shinagawa, T., Nogami, Y., Manabe, R., Ogo, S., Sekine, Y., 2014. Low temperature catalytic reverse water gas shift reaction assisted by
an electric field. Catal. Today 232, 27–32. http://dx.doi.org/10.1016/j.cattod.2013.11.035.
Pakhare, D., Spivey, J., 2014. A review of dry (CO 2 ) reforming of methane over noble metal catalysts. Chem. Soc. Rev. 43 (22), 7813–7837.
http://dx.doi.org/10.1039/C3CS60395D.
Pan, H., Li, Y., Zhu, L., Lu, Y., 2022. Solar-driven H2O/CO2 conversion to fuels via two-step electro-thermochemical cycle in a solid oxide electrochemical
cell. Energy Convers. Manag. 259, 115578. http://dx.doi.org/10.1016/j.enconman.2022.115578.
Pan, Z., et al., 2020. Highly efficient photoelectrocatalytic reduction of CO2 to methanol by a p–n heterojunction CeO2/CuO/Cu catalyst. Nano-Micro
Lett. 12 (1), 18. http://dx.doi.org/10.1007/s40820-019-0354-1.
15
Pasupulety, N., Driss, H., Alhamed, Y.A., Alzahrani, A.A., Daous, M.A., Petrov, L., 2015. Studies on Au/Cu–Zn–Al catalyst for methanol synthesis from
CO2. Appl. Catal. A Gen. 504, 308–318. http://dx.doi.org/10.1016/j.apcata.2015.01.036.
Peter, S.C., 2018. Reduction of CO 2 to chemicals and fuels: A solution to global warming and energy crisis. ACS Energy Lett. 3 (7), 1557–1561.
http://dx.doi.org/10.1021/acsenergylett.8b00878.
Qu, J., Zhou, X., Xu, F., Gong, X.-Q., Tsang, S.C.E., 2014. Shape effect of Pd-promoted Ga2O3 nanocatalysts for methanol synthesis by CO2 hydrogenation.
J. Phys. Chem. C 118 (42), 24452–24466. http://dx.doi.org/10.1021/jp5063379.
Rabee, A.I.M., et al., 2023. Role of interfacial oxygen vacancies in low-loaded Au-based catalysts for the low-temperature reverse water gas shift
reaction. Appl. Catal. B Environ. 321, 122083. http://dx.doi.org/10.1016/j.apcatb.2022.122083.
Rui, N., Wang, Z., Sun, K., Ye, J., Ge, Q., Liu, C., 2017. CO2 hydrogenation to methanol over Pd/In2o3: effects of Pd and oxygen vacancy. Appl. Catal.
B Environ. 218, 488–497. http://dx.doi.org/10.1016/j.apcatb.2017.06.069.
Saputro, A.G., et al., 2021. Density functional and microkinetic study of CO2 hydrogenation to methanol on subnanometer Pd cluster doped by
transition metal (M=Cu, Ni, Pt, Rh). Int. J. Hydrogen Energy 46 (27), 14418–14428. http://dx.doi.org/10.1016/j.ijhydene.2021.02.009.
Sharafutdinov, I., et al., 2014. Intermetallic compounds of Ni and ga as catalysts for the synthesis of methanol. J. Catal. 320, 77–88. http:
//dx.doi.org/10.1016/j.jcat.2014.09.025.
Sharma, I., Shah, V., Shah, M., 2022. A comprehensive study on production of methanol from wind energy. Environ. Technol. Innov. 28, 102589.
http://dx.doi.org/10.1016/j.eti.2022.102589.
Sodiq, A., et al., 2023. A review on progress made in direct air capture of CO2. Environ. Technol. Innov. 29, 102991. http://dx.doi.org/10.1016/j.eti.
2022.102991.
Song, J., et al., 2020. The role of Al doping in Pd/ZnO catalyst for CO2 hydrogenation to methanol. Appl. Catal. B Environ. 263, 118367.
http://dx.doi.org/10.1016/j.apcatb.2019.118367.
Stangeland, K., Kalai, D., Li, H., Yu, Z., 2017. CO2 methanation: The effect of catalysts and reaction conditions. Energy Procedia 105, 2022–2027.
http://dx.doi.org/10.1016/j.egypro.2017.03.577.
Su, X., Yang, X., Zhao, B., Huang, Y., 2017. Designing of highly selective and high-temperature endurable RWGS heterogeneous catalysts: recent
advances and the future directions. J. Energy Chem. 26 (5), 854–867. http://dx.doi.org/10.1016/j.jechem.2017.07.006.
Sun, K., Rui, N., Shen, C., Liu, C., 2021. Theoretical study of selective hydrogenation of CO2 to methanol over Pt4/In2O3 model catalyst. J. Phys. Chem.
C 125 (20), 10926–10936. http://dx.doi.org/10.1021/acs.jpcc.1c00638.
Szanyi, J., Nelson, N., Chen, L., Motta, D., Kovarik, L., 2020. In situ dispersion of Pd on TiO2 during reverse water-gas shift reaction: formation of
atomically dispersed Pd. Angew. Chemie Int. Ed. 59, http://dx.doi.org/10.1002/anie.202007576.
Tada, S., Satokawa, S., 2018. Effect of Ag loading on CO2-to-methanol hydrogenation over Ag/Cuo/ZrO2. Catal. Commun. 113, 41–45. http://dx.doi.
org/10.1016/j.catcom.2018.05.009.
Tang, Y., et al., 2019. Rh single atoms on TiO2 dynamically respond to reaction conditions by adapting their site. Nature Commun. 10 (1), 4488.
http://dx.doi.org/10.1038/s41467-019-12461-6.
Tawalbeh, M., Al-Ismaily, M., Kruczek, B., Tezel, F.H., 2021a. Modeling the transport of CO2, N2, and their binary mixtures through highly permeable
silicalite-1 membranes using maxwell-stefan equations. Chemosphere 263, 127935. http://dx.doi.org/10.1016/j.chemosphere.2020.127935.
Tawalbeh, M., Al Mojjly, A., Al-Othman, A., Hilal, N., 2018. Membrane separation as a pre-treatment process for oily saline water. Desalination 447,
182–202. http://dx.doi.org/10.1016/J.DESAL.2018.07.029.
Tawalbeh, M., Al-Othman, A., Salamah, T., Alkasrawi, M., Martis, R., El-Rub, Z.A., 2021b. A critical review on metal-based catalysts used in the pyrolysis
of lignocellulosic biomass materials. J. Environ. Manag. 299, 113597. http://dx.doi.org/10.1016/j.jenvman.2021.113597.
Tawalbeh, M., Muhammad Nauman Javed, R., Al-Othman, A., Almomani, F., 2022a. The novel advancements of nanomaterials in biofuel cells with a
focus on electrodes’ applications. Fuel 322, 124237. http://dx.doi.org/10.1016/j.fuel.2022.124237.
Tawalbeh, M., Muhammad Nauman Javed, R., Al-Othman, A., Almomani, F., 2023. The novel contribution of non-noble metal catalysts for intensified
carbon dioxide hydrogenation: Recent challenges and opportunities. Energy Convers. Manag. 279, 116755. http://dx.doi.org/10.1016/j.enconman.
2023.116755.
Tawalbeh, M., Murtaza, S.Z.M., Al-Othman, A., Alami, A.H., Singh, K., Olabi, A.G., 2022b. Ammonia: A versatile candidate for the use in energy storage
systems. Renew. Energy 194, 955–977. http://dx.doi.org/10.1016/j.renene.2022.06.015.
Tollefson, J., 2021. Carbon emissions rapidly rebounded following COVID pandemic dip. Nature. England http://dx.doi.org/10.1038/d41586-021-03036-
x.
Toyao, T., Kayamori, S., Maeno, Z., Siddiki, S.M.A.H., Shimizu, K., 2019. Heterogeneous Pt and MoOx co-loaded TiO2 catalysts for low-temperature
CO2 hydrogenation to form CH3OH. ACS Catal. 9 (9), 8187–8196. http://dx.doi.org/10.1021/acscatal.9b01225.
Upadhye, A.A., et al., 2015. Plasmon-enhanced reverse water gas shift reaction over oxide supported Au catalysts. Catal. Sci. Technol. 5 (5), 2590–2601.
http://dx.doi.org/10.1039/C4CY01183J.
van Kampen, J., Boon, J., van Berkel, F., Vente, J., van Sint Annaland, M., 2019. Steam separation enhanced reactions: Review and outlook. Chem. Eng.
J. 374, 1286–1303. http://dx.doi.org/10.1016/j.cej.2019.06.031.
Velty, A., Corma, A., 2023. Advanced zeolite and ordered mesoporous silica-based catalysts for the conversion of CO 2 to chemicals and fuels. Chem.
Soc. Rev. http://dx.doi.org/10.1039/D2CS00456A.
Vu, T.T.N., Desgagnés, A., Iliuta, M.C., 2021. Efficient approaches to overcome challenges in material development for conventional and intensified
CO2 catalytic hydrogenation to CO, methanol, and DME. Appl. Catal. A Gen. 617, 118119. http://dx.doi.org/10.1016/j.apcata.2021.118119.
Wang, J., Sun, K., Jia, X., Liu, C., 2021a. CO2 hydrogenation to methanol over Rh/In2O3 catalyst. Catal. Today 365, 341–347. http://dx.doi.org/10.1016/
j.cattod.2020.05.020.
Wang, L.C., Tahvildar Khazaneh, M., Widmann, D., Behm, R.J., 2013. TAP reactor studies of the oxidizing capability of CO2 on a Au/CeO2 catalyst – A first
step toward identifying a redox mechanism in the reverse water–gas shift reaction. J. Catal. 302, 20–30. http://dx.doi.org/10.1016/j.jcat.2013.02.021.
Wang, W., Tongo, D.W.K., Song, L., Qu, Z., 2021b. Effect of au addition on the catalytic performance of CuO/CeO2 catalysts for CO2 hydrogenation to
methanol. Top. Catal. 64 (5), 446–455. http://dx.doi.org/10.1007/s11244-021-01414-3.
Wang, W., Wang, S., Ma, X., Gong, J., 2011. Recent advances in catalytic hydrogenation of carbon dioxide. Chem. Soc. Rev. 40 (7), 3703–3727.
http://dx.doi.org/10.1039/C1CS15008A.
Wang, F., et al., 2016. Active site dependent reaction mechanism over Ru/CeO2 catalyst toward CO2 methanation. J. Am. Chem. Soc. 138 (19),
6298–6305.
Wang, Y., et al., 2019. Ensemble effect in bimetallic electrocatalysts for CO2 reduction. J. Am. Chem. Soc. 141 (42), 16635–16642.
Wu, Y., et al., 2021. UIO66-membranized SAPO-34 pt catalyst for enhanced carbon dioxide conversion efficiency. Mater. Today Energy 21, 100781.
http://dx.doi.org/10.1016/j.mtener.2021.100781.
Xing, Y., et al., 2021. Single atomic Pt on SrTiO3 catalyst in reverse water gas shift reactions. Catalysts 11 (6), http://dx.doi.org/10.3390/catal11060738.
Xu, H., Li, Y., Luo, X., Xu, Z., Ge, J., 2017. Monodispersed gold nanoparticles supported on a zirconium-based porous metal–organic framework and
their high catalytic ability for the reverse water–gas shift reaction. Chem. Commun. 53 (56), 7953–7956. http://dx.doi.org/10.1039/C7CC02130E.
Yamano, R., Ogo, S., Nakano, N., Higo, T., Sekine, Y., 2023. Non-conventional low-temperature reverse water–gas shift reaction over highly dispersed
Ru catalysts in an electric field. EES Catal. http://dx.doi.org/10.1039/D2EY00004K.
16
Yan, C., et al., 2022. Hybrid composite of subnanometer CoPd cluster-decorated cobalt oxide-supported Pd nanoparticles give outstanding CO
production yield in CO2 reduction reaction. Catalysts 12 (10), http://dx.doi.org/10.3390/catal12101127.
Yang, K., Jiang, J., 2021. Transforming CO2 into methanol with N-heterocyclic carbene-stabilized coinage metal hydrides immobilized in a
metal–organic framework UiO-68. ACS Appl. Mater. Interfaces 13 (49), 58723–58736. http://dx.doi.org/10.1021/acsami.1c18885.
Yang, L., Pastor-Pérez, L., Villora-Pico, J.J., Gu, S., Sepúlveda-Escribano, A., Reina, T.R., 2020. CO2 valorisation via reverse water-gas shift reaction using
promoted Fe/CeO2-Al2O3 catalysts: Showcasing the potential of advanced catalysts to explore new processes design. Appl. Catal. A Gen. 593,
117442. http://dx.doi.org/10.1016/j.apcata.2020.117442.
Yang, X., et al., 2017. Promotion effects of potassium on the activity and selectivity of Pt/zeolite catalysts for reverse water gas shift reaction. Appl.
Catal. B Environ. 216, 95–105. http://dx.doi.org/10.1016/j.apcatb.2017.05.067.
Yusuf, N., Almomani, F., 2023. Highly effective hydrogenation of CO2 to methanol over Cu/ZnO/Al2O3 catalyst: A process economy & environmental
aspects. Fuel 332, 126027. http://dx.doi.org/10.1016/j.fuel.2022.126027.
Zahedi, R., Ayazi, M., Aslani, A., 2022. Comparison of amine adsorbents and strong hydroxides soluble for direct air CO2 capture by life cycle
assessment method. Environ. Technol. Innov. 28, 102854. http://dx.doi.org/10.1016/j.eti.2022.102854.
Zeng, F., et al., 2021. Catalysts design for higher alcohols synthesis by CO2 hydrogenation: Trends and future perspectives. Appl. Catal. B Environ.
291, 120073. http://dx.doi.org/10.1016/j.apcatb.2021.120073.
Zhang, H., Xu, H., Li, Y., Su, Y., 2020a. Octahedral core–shell bimetallic catalysts M@UIO-67 (M = Pt–Pd nanoparticles, Pt–Pd nanocages): Metallic
nanocages that enhanced CO2 conversion. Appl. Mater. Today 19, 100609. http://dx.doi.org/10.1016/j.apmt.2020.100609.
Zhang, X., Yuan, C., Huang, Z., Xu, H., Shen, W., Recent advances in catalytic hydrogenation of Co2 into value-added chemicals over oxide-zeolite
bifunctional catalysts. In: Recent Adv. Catal. Hydrog. Co2 Into Value-Added Chem. over Oxide-Zeolite Bifunctional Catal.
Zhang, Z.-S., et al., 2020b. Intrinsically active surface in a Pt/γ -Mo2N catalyst for the water–gas shift reaction: Molybdenum nitride or molybdenum
oxide? J. Am. Chem. Soc. 142 (31), 13362–13371. http://dx.doi.org/10.1021/jacs.9b11088.
Zhang, N., et al., 2022. A review on oil/water emulsion separation membrane material. J. Environ. Chem. Eng. 107257.
Zhang, C., et al., 2023. Blocking methanation during reverse water gas shift reaction on Ni/SiO2 catalysts by surface Ag. ChemCatChem 15 (3),
e202201284. http://dx.doi.org/10.1002/cctc.202201284.
Zhao, X., Xu, H., Wang, X., Zheng, Z., Xu, Z., Ge, J., 2018. Monodisperse metal–organic framework nanospheres with encapsulated core–shell
nanoparticles Pt/Au@Pd@{Co2(oba)4(3-bpdh)2}4H2O for the highly selective conversion of CO2 to CO. ACS Appl. Mater. Interfaces 10 (17),
15096–15103. http://dx.doi.org/10.1021/acsami.8b03561.
Zhao, Z., et al., 2021. Atomically dispersed Pt/CeO2 catalyst with superior CO selectivity in reverse water gas shift reaction. Appl. Catal. B Environ.
291, 120101. http://dx.doi.org/10.1016/j.apcatb.2021.120101.
Zhong, J., Yang, X., Wu, Z., Liang, B., Huang, Y., Zhang, T., 2020. State of the art and perspectives in heterogeneous catalysis of CO 2 hydrogenation
to methanol. Chem. Soc. Rev. 49 (5), 1385–1413. http://dx.doi.org/10.1039/C9CS00614A.
Ziemba, M., Weyel, J., Hess, C., 2022. Elucidating the mechanism of the reverse water–gas shift reaction over Au/CeO2 catalysts using operando and
transient spectroscopies. Appl. Catal. B Environ. 301, 120825. http://dx.doi.org/10.1016/j.apcatb.2021.120825.
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Environmental Technology & Innovation 31 (2023) 103217

Contents lists available at ScienceDirect

Environmental Technology & Innovation

Unlocking the potential of CO2 hydrogenation into valuable

6. Noble metal catalysts: advantages and drawbacks .............................................................................................................................. 11

Fig. 1. A schematic outline of mechanisms for catalytic CO2 hydrogenation.

2. Outline of CO2 hydrogenation via catalysis

3. Catalytic processes for CO synthesis via RWGS reaction

3.1. The mechanism of surface redox reactions

3.2. The associative mechanism: concept and background

4. Noble metal catalysts for reverse water-gas shift reactions

Fig. 5. A formate-based mechanism over Rh/Al2 O3 catalysts (Heyl et al., 2016).

5. Noble metal-based catalysts: Types and potential

6. Noble metal catalysts: advantages and drawbacks

7. Advancement in catalytic hydrogenation

8. Conclusions and prospects

CRediT authorship contribution statement

Declaration of competing interest

Data will be made available on request.

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