Molecular Catalysis 561 (2024) 114168

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Molecular Catalysis
journal homepage: www.journals.elsevier.com/molecular-catalysis

Review Paper

Glycerol conversion into added-value products on Ni-Cu based catalysts:

Investigating mechanistic variations via catalyst modulation
José L.C. Fajín *, M.Natália D.S. Cordeiro *
LAQV@REQUIMTE, Departamento de Química e Bioquímica, Faculdade de Ciências, Universidade do Porto, Porto P-4169-007, Portugal

A R T I C L E I N F O A B S T R A C T

Keywords: Glycerol (propane-1,2,3-triol), a byproduct of biodiesel production, serves as a valuable precursor for numerous
Ni− Cu catalysts products including hydrogen, propylene glycol (propane-1,2-diol), propane-1,3-diol, lactide, acrolein, hydrox­
Glycerol conversion yacetone, pyruvaldehyde, acetaldehyde, ethylene glycol, glyceraldehyde, lactic acid, acetic acid, formic acid,
Biodiesel production
glyceric acid, tartronic acid, oxalic acid, glycolic acid, glyoxylic acid, and pyruvic acid, among others. Utilizing
Fuel cells
glycerol for the production of these diverse compounds not only enhances the sustainability of biodiesel pro­
Sustainable energy production
duction but also contributes to the economic viability of the entire process.
The primary challenge in realizing the conversion of glycerol into the aforementioned chemicals lies in the
need for catalysts with adequate activity, selectivity, and stability for the various processes involved. To address
this, researchers have frequently employed cost-effective Ni-Cu-based catalysts in studies focused on glycerol
conversion. These catalysts can be effectively modified to adjust their activity, selectivity, and stability, thereby
enabling the conversion of glycerol into valuable products. This review provides a comprehensive overview of
recent achievements related to Ni-Cu catalysts utilized in glycerol conversion to valuable products. It explores
and discusses general principles governing the catalytic properties of these catalysts. Special attention is paid to
the modification of the reaction mechanisms by varying catalyst morphology and composition or adjusting re­
action conditions. These modifications play a crucial role in achieving the desired products effectively. The
knowledge gained on modifying the reaction mechanism by modulating Ni–Cu catalysts can be further utilized in
the design of catalysts with improved characteristics for glycerol conversion.

1. Introduction electricity and are considered environmentally friendly when fueled by

renewable sources. Hydrogen and methanol are particularly valuable
The environmental challenges arising from fossil fuel combustion, fuels for FCs due to their high specific-mass energy density and the
principally the alteration of global climate patterns due to the green­ absence of C–C bonds, which simplifies molecular skeleton cleavage.
house effect, have prompted exhaustive investigations into alternative However, the purity of these fuels is crucial, as even trace amounts of
energy sources to replace carbon, petrol, or natural gas [1]. Therefore, species like COx can poison the platinum-based catalysts used in the
solar panels, wind turbines, and hydroelectric systems are widely electrochemical process even at ppm concentrations [4–6]. Presently,
employed for electricity generation, particularly in regions such as hydrogen is primarily derived from non-renewable sources like methane
China, Europe, and North America [1]. Over the past decades, the (about 95 % of natural gas is methane) [7,8], although alternative
transportation sector has also witnessed experiments with alternative methods involving the reforming of light alcohols or hydrocarbons from
devices and fuels, including fuel cells (FCs) utilizing hydrogen or renewable sources like biomass gasification or fermentation are gaining
methanol, electric engines, and biofuels. Though the significant surge in attention [9–11]. Another way to obtain hydrogen in a renewable
global sales of electric cars, with expectations to exceed 14 million in manner is through the transformation of renewable industrial byprod­
2023 and approximately 18 % of new cars being electric [2], the ucts, such as glycerol (propane-1,2,3-triol), via reforming.
adoption of fuel cells in transportation remains somewhat lagging
despite their promising potential [3].
Fuel cells operate in continuous mode, converting fuels into

* Corresponding authors.
E-mail addresses: [email protected] (J.L.C. Fajín), [email protected] (M.NatáliaD.S. Cordeiro).

https://doi.org/10.1016/j.mcat.2024.114168
Received 31 January 2024; Received in revised form 14 April 2024; Accepted 21 April 2024
Available online 2 May 2024
2468-8231/© 2024 The Authors. Published by Elsevier B.V. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-
nc-nd/4.0/).
J.L.C. Fajín and M.NatáliaD.S. Cordeiro Molecular Catalysis 561 (2024) 114168

1.1. Hydrogen production from glycerol reforming reduces the total gas yield, whereas the addition of KOH enhances gas
yields and hydrogen selectivity [28]. Moreover, glycerol reforming for
Glycerol, the main byproduct of biodiesel production, is obtained in hydrogen production is not limited to fuel cell applications. Instead, it
quantities of 10 tons for every 100 tons of biodiesel produced [12]. can be coupled with other reactions to facilitate the hydrogenation of
While glycerol is primarily consumed in the manufacture of pharma­ chemicals like guaiacol, thereby eliminating the need for external H2
ceuticals and cosmetics [12], its increased production and limited de­ supply [29].
mand have led to its accumulation. Glycerol production had increased
fastly following the rise in biodiesel production up to 2020, with 39.03 1.2. Glycerol hydrogenolysis toward propane-1,2-diol and propane-1,3-
billion liters produced that year. Production remained almost stable diol
from 2020 to 2022 (at 38.51 billion liters of biodiesel), largely due to the
effects of Covid-19 on the global market. However, it is expected that Hydrogen can act also as a reactant in hydrogenolysis reactions un­
global biodiesel and crude glycerol production will grow by 17.5 % dergone by glycerol. To achieve this, obtaining hydrogen in situ is ad­
annually during the period 2023–2027 [13]. vantageous, as it is a valuable chemical, and external supply of this gas
Therefore, one potential application of this byproduct is its conver­ would necessitate high pressures. Thus, alcohols, organic acids, hydro­
sion into hydrogen through reforming. For more details about its pro­ carbons, or even glycerol itself can be inserted into the reaction medium
duction, refer to the scheme in Fig. 1 [14,15]. The glycerol reforming to produce H2 “in situ” through their reforming.
process is typically an endothermic process, requiring high temperatures The primary products obtained from glycerol through its hydro­
and significant vaporization energy for reactants [14]. Hence, catalysts genolysis are propane-1,2-diol (propylene glycol) or propane-1,3-diol.
with appropriate activity to catalyze such a reforming process are Propylene glycol finds significant industrial applications as a heat
needed. In particular, Ni–Cu catalysts exhibit superior catalytic activity transfer medium, viscosity controller, solvent for active compounds,
for glycerol reforming, outperforming other bimetallic combinations moisture regulator, and corrosion inhibitor. Propane-1,3-diol is used as a
like Ni–Co or Ni–Zn [16,17], as well that of a parent monometallic bulk chemical in synthesizing compounds like polyesters, polyethers, or
catalyst (e.g.: Ni) [18,19]. To reduce energy consumption, the reforming polyurethanes. Ni–Cu based catalysts have demonstrated their efficacy
reaction is carried out in liquid phase at lower temperatures [20]. In in the conversion of glycerol to the aforementioned chemicals through
doing so, the Ni− Cu catalyst is supported in CeO2 to form a mesoporous hydrogenolysis reactions. Several studies have focused on utilizing
phase, and CaO sorbent is added to capture the CO2 product and shift the hydrogen donors in glycerol hydrogenolysis towards propane-1,2-diol
equilibrium toward H2 [20]. The addition of Cu to the Ni phase pro­ using Ni-Cu-based catalysts. The efficacy of propane-2-ol [30], formic
motes the water gas shift reaction (WGS: CO+H2O → CO2+H2), shifting acid [31–33] and methanol [34,35] as donors to generate H2 in the re­
additional H2 from water, while limiting undesired methanation reac­ action medium has been demonstrated.
tion catalyzed by Ni patches [19–25]. Besides, hydrogen yields can be However, when hydrogen generated in situ is used, glycerol con­
enhanced by displacing the equilibrium of the WGS reaction, either by version and selectivity towards propane-1,2-diol are typically lower [36,
incorporating additional components into the catalyst’s active phase or 37]. Importantly, hydrogen generated in situ is obtained through
the reaction medium to trap the CO2 product [26]. The selectivity to­ reforming of the donor on the catalytic surface, while the hydrogenolysis
wards CO can be reduced to even ppm levels (less than 30 ppm) by reaction progresses through the acetol intermediary (acid route). The
introducing spacers such as Al12Ga14O33 oxide, which prevents sintering hydrogenation towards propane-1,2-diol is usually the rate-limiting step
of the catalyst’s active phase [26]. Another relevant aspect in the glyc­ due to the limited amounts of hydrogen in the reaction medium [37].
erol reforming process is the impact of temperature on the conversion Thus, acetol yields increase when there is not enough hydrogen in the
and selectivity; while higher reaction temperatures may improve glyc­ reaction medium (low reforming rates), whereas if the basic route is
erol conversion, they reduce selectivity towards hydrogen [20]. Alter­ favored, lactic acid production can reach up to 50 % [37]. Following the
natively, electromagnetic radiation can provide the energy needed for basic route, up to 31.8 % of propane-1,2-diol can also be produced if the
glycerol reforming on Ni–Cu-based catalysts, resulting in hydrogen Ni-Cu/NaY (zeolite) catalyst is used [38]. Nonetheless, if external H2 is
production rates surpassing those achieved with noble metal-based used in glycerol hydrogenolysis towards propane-1,2-diol, higher glyc­
catalysts [27]. erol conversion and selectivity towards propane-1,2-diol are achieved
Finally, it is crucial to bear in mind that crude glycerol, a byproduct [36,39–49], but this process has the inconvenience of requiring high
of biodiesel production, contains various impurities such as soap, alkali, pressure to supply the hydrogen reactant, along with associated costs
ester, salts, and other organic compounds. Therefore, evaluating their and flammability concerns.
impact on the reforming process is essential. [28]. Experimental findings
indicate that methanol has no significant impact on glycerol reforming.
Conversely, the presence of ethanoic acid in the reaction medium

Fig. 1. Scheme showing the main steps in the biodiesel production, including the glycerin byproduct formation.

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J.L.C. Fajín and M.NatáliaD.S. Cordeiro Molecular Catalysis 561 (2024) 114168

1.3. Glycerol conversion to other products Table 1

Summary of value-added products from glycerol: reaction route and catalyst
Ni− Cu/γ-Al2O3 can also be employed in the production of various used to obtain each product.
chemicals. For example, at 543 K and atmospheric pressure, the main Chemical product Reaction route Catalyst/s References
products obtained from glycerol conversion include hydroxyacetone, Hydrogen Glycerol steam Ni− Cu/attapulgite [16]
pyruvaldehyde, lactide, lactic acid, acetic acid, pyruvic acid, methane, reforming (GSR). Ni− Cu/La2O3-MgO [17]
ethylene glycol, acetaldehyde, and traces of propane-1,2-diol and furan Ni10− Cu5/ [26]
derivatives [50]. Yet, the catalyst selectivity is highly dependent on the Ca12Al14O33–CaO
Glycerol aqueous Ni− Cu2/MgO–CaO [16]
Ni/Cu ratio. Indeed, on monometallic Ni catalyst, CH4 selectivity is close
phase reforming Ni1− Cu12/MWCNT [19]
to 100 %. However, increasing the Cu ratio progressively decreases CH4 (GAPR). (Multiwalled carbon [20]
selectivity due to the lack of contiguous Ni atoms necessary for methane nanotubes) [23]
formation. Simultaneously, selectivity toward dehydration products, Ni1− Cu2/ [28]
such as pyruvaldehyde and hydroxyacetone, increases [50]. Other CeO2+0.2gCaO
Ni1− Cu12/MWCNT
chemicals, including acetaldehyde, pyruvic acid, acetic acid, ethylene (Multiwalled carbon
glycol, lactide, or lactic acid, are favored by specific Cu/Ni ratios related nanotubes)
to the total number of exposed Ni and Cu sites [50]. Moreover, Ni− Cu/CeO2 plus
combining Ni− Cu/γ-Al2O3 catalyst with Pt/C catalyst leads to a reactive KOH
Propane-1,2-diol Glycerol dehydration Ni− Cu/TiO2 [30]
system with good glycerol conversion and selectivity toward CO, CH4, or
to acetol + acetol Ni− Cu/ZnO/Al2O3 [34− 35]
other hydrocarbon gases, allowing the gasification of glycerol [51]. hydrogenation to Ni− Cu/Al2O3 [36,
Furthermore, anodic glycerol electrooxidation and cathodic nitrate propane-1,2-diol Ni− Cu/ZSM-5 41− 46]
reduction on Ni− Cu based catalysts produce formic acid and ammonia, (zeolite) [36]
respectively, under a low cell potential of 1.37 V at 100 mA cm‒2 current Ni− Cu/30 %MgO- [37]
Al2O3 [39]
density [52]. Besides, Ni− Cu nanoparticles supported on active carbon
Ni− Cu(3 %)/SiO2 [40]
felt are capable of producing formic acid through glycerol electro­ Ni− Cu/M-SAPO-11 [48]
oxidation with a selectivity of up to 97.4 % [53]. Other experiments (zeolite) [49]
focused on glycerol electrooxidation have detected the formation of a Ni− Cu/AC(active
carbon)
series of organic acids, i.e.: oxalic, glyoxylic, formic, glycolic acids, etc.
Ni− Cu/SiO2
The formation of these acids is also favored in Ni-based alloys like Formation of a Ni− Cu/Al2O3 [31− 33]
Ni− Cu [54]. secondary alkoxide
on the support +
2. Analysis and discussion alkoxide
hydrogenation to
propane-1,2-diol
As outlined, glycerol can indeed be converted into valuable products Glycerol Ni− Cu/NaY(zeolite) [38]
such as, hydrogen, propylene glycol (propane-1,2-diol), propane-1,3- dehydrogenation to
diol, lactide, acrolein, dihydroxyacetone, pyruvaldehyde, acetalde­ glyceraldehyde +
dehydration to 2-
hyde, ethylene glycol, glyceraldehyde, or lactic, acetic, formic, and
hydroxypropenal +
pyruvic acids, among others. However, the main challenge in converting hydrogenation to
glycerol into these valuable products lies in the limited activity, selec­ propane-1,2-diol
tivity, or stability of catalysts commonly used for such processes. (basic route)
Additionally, the cost associated with catalysts based on highly reactive Lactic acid Glycerol Ni− Cu/MgO [37]
dehydrogenation to
materials, such as noble or rare metals, poses a limitation.
glyceraldehyde +
To address these challenges, catalysts based on the inexpensive Ni‒ dehydration to
Cu bimetallic combination are being developed for the conversion of pyruvaldehyde +
glycerol into a range of valuable products. Researchers are carefully hydration to lactic
acid (basic route)
modulating the catalyst composition, morphology, or reaction condi­
Glycerol dehydration Ni− Cu/γ-Al2O3 [50]
tions to achieve the desired product(s). This article critically reviews to hydroxyacetone +
recent achievements in glycerol conversion towards valuable products hydroxyacetone
using cost-effective Ni‒Cu catalysts. It aims to elucidate the general dehydrogenation to
rules governing the reactivity of these catalytic systems, with special pyruvaldehyde +
pyruvaldehyde
attention given to the reaction mechanisms that explain products for­
hydration to lactic
mation and how these mechanisms are influenced by modifications to acid
the catalyst structure, composition, or reaction conditions. Table 1 Methane Deep hydrogenolysis Ni− Cu/γ-Al2O3 [50]
summarizes the reaction routes and Ni‒Cu based catalysts used in the of glycerol (high Ni
contents)
works reviewed here to obtain value-added products from glycerol.
Hydroxyacetone Glycerol dehydration Ni− Cu/γ-Al2O3 [50]
Pyruvaldehyde Hydroxyacetone Ni− Cu/γ-Al2O3 [50]
2.1. Hydrogen production through glycerol reforming: reaction dehydrogenation
mechanism and catalyst optimization Lactide Lactic acid Ni− Cu/γ-Al2O3 [50]
dimerization
Pyruvic acid Pyruvaldehyde Ni− Cu/γ-Al2O3 [50]
Hydrogen is a valuable chemical with applications as fuel in fuel cells hydration to pyruvic
due to its high specific-mass energy density. It is also utilized as a acid
reactant in hydrogenation/hydrogenolysis reactions and as a chemical Acetic acid plus Hydroxyacetone Ni− Cu/γ-Al2O3 [50]
reducer in various redox processes. Renewable production of hydrogen formic acid hydrogenation to
acetaldehyde plus
can be achieved through processes such as water splitting or the
formaldehyde +
reforming of organic compounds obtained renewably [55]. As previ­
(continued on next page)
ously mentioned, glycerol, for instance, a byproduct of biodiesel pro­
duction, can serve as a renewable source for hydrogen production.

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Table 1 (continued ) Table 2

Chemical product Reaction route Catalyst/s References
Features for most recent investigations on hydrogen production by glycerol
reforming on Ni− Cu based catalysts.
hydration to acetic
and formic acids Catalyst Glycerol H2 selectivity Reference
Formic acid plus Electrochemical NiCu-OH [52] conversion
ammonia oxidation/reduction Ni− Cu/attapulgite 98.5% (at 600 68.9% (at 600 ◦ C) [16]
of glycerol and ◦
C)
nitrate Ni− Cu/La2O3-MgO 84.5% (at 500 96.1 % (at 500 ◦ C) [17]
Formic acid Glycerol Ni1Cu1@ACF(Active [53] ◦
C)
electrooxidation carbon felt) Ni− Cu2/MgO–CaO ~ 66 % (at 240 ~ 85% (at 240 C) ◦
[18]
Oxylic, glycolic, Glycerol Ni− Cu/CCE(carbon- [54] ◦
C)
glyoxylic, formic, electrooxidation ceramic electrodes) Ni1− Cu12/MWCNT a
84% (at 240 ◦ C) 86% (at 240 ◦ C) [19]
hydroxypyruvic, Ni1− Cu2/CeO2+0.2gCaO ~ 50% (at 225 ~ 98% (200 to 225 [20]
ketomalonic, ◦
C) ◦
C)
oxalic, tartronic, Ni1− Cu12/MWCNTa 84% (at 250 ◦ C) 85.6% (at 250 ◦ C) [23]
ketomalic and Ni10− Cu5/ ~ 98% (525 ◦ C) 97% (525 ◦ C) [26]
glyceric acids Ca12Al14O33–CaO
Ni− Cu/CeO2 plus KOH ~ 60% (at 240 ~ 90% (240 ◦ C) [26]
◦
C) ~ 95% (200 ◦ C)
Theoretically, the reforming of one mole of glycerol produce four moles ~ 50% (at 200
of hydrogen but three C − C bonds have to be broken during the com­ ◦
C)
plete glycerol decomposition. This is a disadvantage compared to the a
MWCNT: Multiwalled carbon nanotubes.
hydrogen produced from methane or methanol, where these bonds are
not present. Therefore, highly active catalysts are needed in glycerol
nanoparticles supported on multiwalled carbon nanotubes suppresses
reforming. In this context, Ni–Cu-based catalysts are actively being
the methanation reaction and enhances performance in H2 formation.
investigated for the reforming of organic compounds, including light
This is due to the preferential catalysis of CO conversion to CO2 by the
alcohols [56,57] and optimized for glycerol reforming as well [14,15].
WGS reaction, rather than CO hydrogenation to methane through the
Hydrogen produced from glycerol must be of high purity for use in
methanation reaction [19,23]. Similar achievements were observed for
FCs. Specifically, the formation of CO needs to be avoided, as it can
glycerol reforming on Ni–Cu supported on mesoporous CeO2 [20] or on
poison the platinum-based catalysts utilized in these devices [4–6]. In
Ce-Sm-xCu (x = 5, 7, 10 at.%) [22], where the formation of the bime­
addition, byproducts of the reforming process, such as methane or coke, tallic phase suppresses methanation and enhances the WGS reaction.
should be minimized. Methane, for example, consumes hydrogen in its
But, how does the formation of the bimetallic Ni− Cu alloy suppress the
formation, while coke can poison the reforming catalyst. Moreover, the methanation reaction and catalyze the WGS reaction? To understand
reforming of glycerol is more favorable when carried out in the aqueous
this, it should be noted that WGS is promoted by copper surfaces [60]
phase (glycerol aqueous phase reforming, GAPR) to avoid the vapor­ whereas the methanation of CO or CO2 by nickel surfaces [56]. There­
ization of reactants, which consumes significant amounts of energy [14,
fore, the formation of the bimetallic alloy is expected to override the
20]. In glycerol reforming process the preferential break of C − C, O − H methanation sites and provide catalytic sites on the surface capable of
and C − H bonds over C − O is crucial which it is favored on metallic
promoting the WGS reaction. This is in line with the results obtained by
sites where atoms of Ni, Cu or Co are present [58]. Ni sites on SiO2 are Dang et al. [26], where the suppression of CO methanation is observed
the most reactive for GR [58] but they suffer strong deactivation by coke
when Cu is palatine incorporated into the Ni matrix. Specifically, Cu
deposition, reason why bimetallic catalysts with improved characteris­ incorporation to Ni enhances CO adsorption, suppressing the C–O bond
tics are being developed, as those based on Ni–Cu. These catalysts offer
break, which is necessary for CO hydrogenation toward methane [61].
the obvious advantage of being cost-effective and abundant compared to
those based on noble or scarce metals. Additionally, modifying the
2.1.2. Temperature impact on glycerol reforming
active phase based on Ni by incorporating Cu helps restricting the
The reaction temperature is another factor that influences the
extension of Ni sites, thereby preventing the formation of undesired
hydrogen yields obtained in glycerol reforming. Generally, it is observed
products such as methane or coke during the reforming process towards
that glycerol reforming rates rise with increasing reaction temperatures,
H2 [57]. What is more, the formation of Ni− Cu alloy prevent the sin­
yet a notable trend emerges: hydrogen selectivity is also higher at lower
tering of the active phase nanoparticles, which is one of the principal
temperatures [16,18,20]. This trend can be ascribed to the easier
factors contributing to the deactivation of Ni-based catalysts [59].
cleavage of C–C, C–H, and C–O bonds at higher temperatures, promoting
Table 2 provides a summary of the most relevant parameters for the
glycerol conversion, while the less favorable WGS reaction contributes
production of hydrogen on Ni–Cu based catalysts considered in this
to a decline in hydrogen selectivity [16]. Considering these insights, an
work.
optimal temperature for H2 production has been proposed to strike a
balance between maximizing glycerol conversion and maintaining high
2.1.1. Catalyst composition and morphology effects
hydrogen selectivity. For example, 225 ◦ C is recognized as an optimal
The superior performance of Ni–Cu-based catalysts in glycerol
temperature for glycerol reforming towards H2 on Ni− Cu/MgO [18] and
reforming catalysis, compared to parent monometallic ones [18,19] and
Ni− Cu/CeO2 [20] catalysts.
those based on other bimetallic combinations like Ni–Co [16,17] or
Ni− Zn [16], has been attributed to factors such as a strong interaction
2.1.3. Impurity influence in crude glycerol reforming
between Ni and Cu [19], the lower particle size in relation to that of
Impurities found in crude glycerol, such as soap, alkali, ester, salts,
monometallic Ni-based catalysts, and the suppression of active metal
and other organic compounds, can significantly impact the catalytic
reducibility due to increased interaction with the support [16,17].
activity of Ni− Cu catalysts. To explore this, Wu et al. [28] investigated
Despite Ni–Cu nanoparticles being larger than those of Ni–Co or Ni–Zn,
the effect of methanol, ethanoic acid and KOH in the reforming of
they exhibit higher reducibility, suggesting an optimal size and reduc­ glycerol on Ni− Cu/CeO2. The authors found that the presence of
ibility for promoting glycerol reforming and the water-gas shift reaction
methanol during glycerol reforming does not alter the total volume of
[16]. Ni–Cu bimetallic nanoparticles supported on attapulgite show gases produced. However, KOH promotes H2 formation, increasing both
lower sintering behavior and coke deposition than other bimetallic
the total H2 yield and hydrogen selectivity. Conversely, the presence of
combinations [16]. Furthermore, the presence of Cu on Ni− Cu ethanoic acid in the reaction medium diminishes hydrogen formation

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J.L.C. Fajín and M.NatáliaD.S. Cordeiro Molecular Catalysis 561 (2024) 114168

rates due to the loss of Ni sites during hydrogen evolution and a shift in glycerol reforming towards H2 and CO2 cannot be overlooked. In fact,
the reaction path. Indeed, the findings from this study can be elucidated this reaction is crucial as it enables the conversion of CO into CO2
by considering the reaction path under acidic (acetic acid) or basic meanwhile shifting additional hydrogen from water. It is also worth
(KOH) conditions. In so doing, the authors employed mechanisms pre­ noting that achieving a hydrogen yield with an extremely low CO con­
viously proposed for aqueous-phase glycerol reforming on other cata­ centration is imperative for FC applications. Even at ppm levels, CO can
lysts [62–65] to analyze the results obtained (see Fig. 2). Under basic act as a catalyst poison for platinum catalysts used in these devices
conditions, glycerol primarily follows the route leading to methanol, [4–6]. Consequently, catalysts that either prevent CO formation or
involving two dehydrogenations of glycerol and ethylene glycol species. efficiently convert the formed CO to CO2 through WGS are essential.
Methanol can also undergo dehydrogenation through reforming, Copper surfaces have been consistently associated with effective
yielding additional hydrogen. Therefore, this pathway comprises the catalysis for the WGS reaction [7,60,66]. Consequently, it is not sur­
dehydrogenation of glycerol to glyceraldehyde, decarbonylation to prising that the inclusion of copper atoms into Ni-based catalysts en­
ethylene glycol, further decarbonylation, and dehydrogenation to pro­ hances their performance in facilitating this reaction. Indeed, the
duce methanol. Additional hydrogen is obtained from methanol observable trend is that an increase in the Cu/Ni ratio in Ni− Cu based
reforming [28]. Alternatively, ethylene glycol can undergo dehydration catalysts promotes WGS catalysis while diminishing CO methanation
to acetaldehyde, which further evolves into acetic acid in the aqueous [19,20,22,23,26]. A comprehensive understanding of the molecular
phase or is hydrogenated to ethanol (refer to Fig. 2 for mechanism de­ mechanism of WGS on nickel-copper surfaces is thus a subject that re­
tails). However, under acidic conditions (acetic acid), this path is not the quires further elucidation. Fig. 3 illustrates a scheme depicting the po­
primary one, as acetic acid is introduced as one of the reaction products tential reaction routes, including redox or associative pathways, for WGS
[28]. Instead, glycerol follows the path of dehydration to produce on nickel-copper sites.
hydroxyacetone, which is then hydrogenated to propane-1,2-diol. The The WGS reaction starts with the dissociation of water on the cata­
latter undergoes hydrogenolysis towards ethanol (see Fig. 2), and since lytic surface, leading to OH+H; this step is identified as the rate-
the reforming of ethanol is more challenging than that of methanol, the determining step on both copper surfaces [60,66] and on Ni− Cu sur­
production of H2 is lower [28]. faces [57]. Notably, the activation energy barrier for water dissociation
on Ni− Cu surfaces closely aligns with that of the highly reactive
2.1.4. Modifiers addition to Ni− Cu based catalysts monometallic Cu(321) surface [57–60]. Additionally, this step exhibits
The activity of Ni− Cu catalysts can be adequately modified by strong structure sensitivity. The presence of low-coordinated atoms on
incorporating other components into the catalyst’s active phase. For the surface, such as those found in surface defects, significantly reduces
instance, the addition of CaO enhances H2 production by trapping the the energy barrier required to extract the first hydrogen from water
CO2 produced through the WGS reaction, resulting in a displacement of [60]. Hence, a higher abundance of surface defects enhances WGS re­
the equilibrium towards the production of CO2 plus H2 [26− 28]. action catalysis, leading therefore to increased CO2 and H2 formation.
Another significant impact of CaO addition is the substantial reduction It’s important to note that catalysts with a lower particle size inherently
of CH4 selectivity to negligible values, as CO is preferentially converted present a higher concentration of surface defects.
to CO2 through the WGS reaction [20]. Furthermore, additives such as Following the initial water dissociation, the OH radical can engage in
Ga and Al play a role in mitigating CO by forming an Al12Ga14O33 oxide. two distinct reactions on the catalytic surface. It can either react with CO
This oxide acts as a spacer among the active phase nanoparticles to form surface species such as carboxyl (in an associative mechanism) or
(Ni− Cu), avoiding their sintering and thereby preserving the integrity of undergo a new dissociation to yield O + H adsorbed on the surface (in a
the catalyst’s active phase [26]. The combined effect of the spacer, CaO redox mechanism) [60]. Subsequently, via the redox mechanism, mon­
sorbent, and the Ni–Cu active phase contributes to the production of H2 oatomic oxygen reacts with CO to produce CO2 while two hydrogen
with very low CO concentrations (less than 30 ppm) [26]. atoms combine to form H2. If the associative mechanism is followed
instead, the carboxyl intermediate formed by the reaction between hy­
2.1.5. Water-gas shift reaction mechanism on copper and Ni− Cu surfaces droxyl and carbon monoxide progresses toward CO2. This can occur
At this stage, the role of the WGS reaction (CO+H2O → CO2+H2) in either through the direct dissociation of COOH on the surface or with the

Fig. 2. Reaction network for glycerol conversion on Ni− Cu catalysts; it was elaborated starting from the mechanisms proposed in Refs. [28,62–65].

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J.L.C. Fajín and M.NatáliaD.S. Cordeiro Molecular Catalysis 561 (2024) 114168

Fig. 3. Reaction network for water gas shift reaction on Ni− Cu catalytic surfaces; redox mechanism vs associative mechanism.

assistance of an OH species, which reduces the energy barrier for the on combed Ni@Cu(110) ones, which allows to account for the effect of
carboxyl evolution toward carbon dioxide [60]. Furthermore, H2 is also low coordinated atoms in catalysis [57]. The results from this study
obtained by the combination of two hydrogen atoms, as in the redox indicate that flat surfaces are capable of catalyzing methanol steam
mechanism. Interestingly, on highly reactive monometallic Cu(321) reforming, and given their greater stability and abundance compared to
surfaces, the associative mechanism is favored over the redox mechanism combed or stepped surfaces, they are likely responsible for the majority
[60]. This preference is consistent with results observed for the WGS of the catalytic activity. On flat Ni@Cu(111) surfaces, methanol steam
reaction on a stepped Ni@Cu(110) surface. On the flat Ni@Cu(111) reforming proceeds through methanol decomposition on the surface,
surface, both mechanisms are nearly equally probable [57]. DFT leading to the formation of CO species [57]. The high energy barrier for
methods also permitted the derivation of reaction descriptors for the CO desorption prevents its release from the surface, making feasible its
WGS reaction on metallic catalytic systems; that is, on monometallic and conversion to CO2 through the WGS reaction [57]. Additionally, water
bimetallic (including Ni− Cu) surfaces, on nanoparticles and nanotubes dissociation, the first step of the WGS reaction, is identified as the
[67–71]. Thus, the adsorption energy of water dissociation reaction rate-limiting step for methanol steam reforming on flat Ni@Cu(111)
products (OH+H) is a good descriptor of WGS reaction on those catalytic surfaces [57]. This finding is particularly important as it allows for the
systems, allowing an easy and fast screening of catalysts for this reaction use of previously derived descriptors for water dissociation [67–72] in
[67–72]. Note that, water dissociation (first step of WGS) is also the rate screening catalysts for methanol steam reforming or the WGS reaction.
determining step of MSR on flat Ni@Cu surfaces, being also predictable Direct CO2 formation from methanol is associated with combed
the validity of reaction descriptors determined for WGS in the screening surfaces. However, as mentioned earlier, these surfaces are less abun­
of catalysts for MSR [57]. dant than flat ones, and their contribution to the catalysis of methanol
steam reforming is lower compared to flat surfaces. Importantly, the
2.1.6. Methanol steam reforming mechanism on Ni− Cu surfaces reaction pathways leading to methane and coke formation on Ni− Cu
Another noteworthy aspect during glycerol reforming is the addi­ surfaces are less favorable than reforming routes, and the formation of
tional production of hydrogen through the reforming of methanol spe­ both species is blocked in these type of bimetallic catalysts [57].
cies. Methanol is derived from glycerol via intermediaries such as A scheme showing the most favorable path for the methanol steam
glyceraldehyde, ethylene glycol, and glycolaldehyde (refer to the reforming on flat Ni− Cu surfaces is depicted in Fig. 4. Methanol
Scheme in Fig. 2 for reaction mechanism details) [28,63]. Methanol can decomposition on the surface proceeds through the CH2OH, CHOH,
also be obtained from the hydrogenation of formaldehyde, formed CHO and CO intermediaries, followed by the WGS reaction. The sub­
through retro-aldol condensation of glyceraldehyde (see Scheme in sequent evolution of the WGS reaction through either the redox or
Fig. 2). In this case, hydrogen is produced during glyceraldehyde for­ associative mechanism is equally favorable on these surfaces [57].
mation but is consumed in formaldehyde hydrogenation, and H2 can As summary of Section 2.1, the incorporation of Cu into high reactive
only be obtained through methanol reforming. Therefore, it is crucial to Ni-based catalysts for glycerol reforming modulates properly the cata­
discern how Ni− Cu catalysts catalyze methanol steam reforming reac­ lyst activity toward desirable products (H2 and CO2). This is done by the
tion. A recent study in our group addressed this topic, investigating the promotion of WGS reaction which converts CO to CO2 and the sup­
methanol steam reforming mechanism on flat Ni@Cu(111) surfaces and pression of side reactions leading to undesirable products as coke

6
J.L.C. Fajín and M.NatáliaD.S. Cordeiro Molecular Catalysis 561 (2024) 114168

Fig. 4. Most favorable reaction route for the methanol steam reforming on Ni− Cu catalysts. For details concerning to less favorable reaction routes and those driving
to secondary byproducts, please see Fig. 1 in Ref. [57].

(catalyst poison) or methane (hydrogen consumption). The use of CO2 hydrogen production with the aim of fueling FCs, glycerol can also serve
sorbents as CaO facilitates the production of H2 free of CO by the as a reactant in various hydrogenation or hydrogenolysis reactions for
displacement of the equilibrium toward this chemical during the WGS different purposes. For instance, hydrogen produced through glycerol
reaction [26–28]. reforming on Ni− Cu based catalysts has been employed in the hydro­
Methanol steam reforming is a crucial step of glycerol reforming genation of guaiacol [29] or in the hydrogenolysis of glycerol itself,
since under basic conditions the glycerol decomposition toward this leading to propane-1,2-diol [36,37]. Producing the last chemical via
species is favored, being the hydrogen yield obtained higher than that renewable means is highly convenient, considering that nowadays it is
obtained under acid conditions where ethanol selectivity is favored primarily produced in non-renewable mode through the hydrolysis of 1,
[28]. DFT method allowed the derivation of reaction descriptors for 2-epoxypropane, a petroleum-derived compound. Additionally, this
WGS that are also valid for MSR and that can be used in the screening of process is highly energy-intensive.
catalysts. Instead, the reaction temperature also influences significantly This section explores the key achievements concerning the mecha­
the Ni− Cu based catalysts performance for the catalysis of glycerol nism for propane-1,2-diol formation on Ni− Cu catalysts, examining how
reforming toward H2, being possible to set an optimal temperature of reaction conditions, catalyst composition and morphology influence the
225 ◦ C for the reaction on Ni− Cu based catalysts supported on MgO [18] catalytic activity. As already mentioned, these bimetallic catalysts offer
and CeO2 [19] oxides. At this temperature, the high conversion of several advantages, including good performance for reforming processes
glycerol which is related to easy breaking of bonds in the glycerol, is (e.g., H2 production), affordability, and high thermal stability. Addi­
combined with a high catalytic performance for the WGS reaction which tionally, they exhibit proficiency in the C − O bond hydrogenolysis re­
is greater at low temperatures. In any case, the generalization of this action, thanks to the presence of the Cu component [31].
achievement to glycerol reforming on Ni− Cu based catalysts is limited The hydrogenolysis of glycerol demands the presence of hydrogen in
by the low number of catalysts considered in the analysis of the influ­ the reaction medium, which can be supplied externally or generated in
ence of temperature in the catalysis. situ by reforming organic acids or alcohols, like formic acid, methanol,
or propane-2-ol [30–35]. The latter option is preferable due to the
high-pressure requirement for externally supplied hydrogen, coupled
2.2. Glycerol hydrogenolysis: conversion, selectivity and mechanism
with its inflammable nature and potential for explosions. Nevertheless,
glycerol hydrogenolysis using external hydrogen results in higher
Despite the preceding discussion focused on glycerol reforming for

7
J.L.C. Fajín and M.NatáliaD.S. Cordeiro Molecular Catalysis 561 (2024) 114168

conversion and propane-1,2-diol selectivity [36–47]. Table 3 summa­ a hydrogen atom during adsorption. Subsequently, the adsorbed glyc­
rizes the most relevant parameters for glycerol hydrogenolysis on Ni− Cu erol undergoes dehydration through the reaction of one of its terminal
based catalysts. hydroxyls with a hydrogen atom adsorbed on the Ni− Cu surface, ob­
tained from formic acid dehydrogenation on bimetallic surfaces
2.2.1. In situ hydrogen generation: mechanism and performance [31–33]. Hence, propane-1,2-diol formation takes place in the inter­
optimization phase between the bimetallic nanoparticle and the oxide.
Moving on to the works where in situ-generated hydrogen is used, Cai Methanol can serve as a hydrogen donor, and this is particularly
et al. [30] tested a broad array of Ni− Cu-based catalysts for glycerol advantageous as it is naturally present in crude glycerol. The Ni− Cu/
conversion to propane-1,2-diol, employing propane-2-ol as the ZnO/Al2O3 catalyst demonstrates excellent activity in glycerol hydro­
hydrogen source. Among these catalysts, Ni− Cu bimetallic nano­ genolysis towards propane-1,2-diol in the presence of methanol. This
particles supported on TiO2 oxide exhibited the highest reactivity and catalyst efficiently catalyzes glycerol dehydration, acetol hydrogena­
selectivity for glycerol hydrogenolysis. The catalyst’s activity was linked tion, and methanol steam reforming simultaneously [34]. Details about
to high Cu dispersion and the Cu/Ni ratio on the surface. However, this the mechanism involved in these reaction routes can be seen in Figs. 2
catalyst experienced significant deactivation due to nanoparticle sin­ and 4. The addition of Ni to Cu/ZnO/Al2O3 enhances propane-1,2-diol
tering, metal leaching, or adsorbed species on the catalytic surface [30]. selectivity by promoting hydrogen formation through methanol steam
The maximum selectivity toward propane-1,2-diol reached 89.7 % for reforming and acetol hydrogenation. Additionally, it helps limiting side
this catalyst, and complete glycerol conversion was achieved when the reactions that might otherwise reduce propane-1,2-diol selectivity.
solvent was propane-2-ol [30]. Propane-1,2-diol formation on the However, this enhancement comes at the cost of a reduction in total
Ni− Cu/TiO2 catalyst occurred through an acetol intermediary, regard­ glycerol conversion due to the loss of specific Cu surface and the for­
less of whether in situ or external hydrogen sources were used [30]. mation of strong acidic sites [34]. Furthermore, propane-2-ol has also
However, the kinetics of the reaction differed based on the hydrogen been successfully employed as a hydrogen donor in glycerol hydro­
source. When external hydrogen was employed, the rate-determining genolysis on Ni− Cu/ZnO/Al2O3, giving rise to a glycerol conversion of
step was the dehydration step, i.e.: the formation of acetol. In contrast, 82.0 % and a propane-1,2-diol selectivity of 86.7 % [35].
when hydrogen generated from propane-2-ol was employed, the key The use of a hydrogen donor in glycerol hydrogenolysis towards
step was the formation of hydrogen for acetol hydrogenation [30]. propane-1,2-diol becomes unnecessary if the catalyst can extract
Acetol also appeared among the products due to incomplete acetol hy­ hydrogen from glycerol through its reforming. Following this, both
drogenation toward propane-1,2-diol, with details about the mechanism Ni− Cu/Al2O3 and Ni− Cu/ZSM-5 catalysts can catalyze equally glycerol
depicted in Fig. 2. reforming and hydrogenolysis. The glycerol conversion on these cata­
Moreover, on Ni− Cu/Al2O3 catalyst, the utilization of formic acid as lysts reaches 80 % and 85 %, respectively, with a propane-1,2-diol
a hydrogen donor resulted in higher yields of propane-1,2-diol selectivity of about 25 % in both cases [36]. A similar selectivity to­
compared to when methanol or propane-2-ol are employed [31–33]. wards propane-1,2-diol is achieved over an extended period with the
This catalyst achieved a glycerol conversion of 90 % and a selectivity of Ni− Cu/30 %MgO-Al2O3 catalyst [37]. In the later catalysts, glycerol
82 % at 493 K [31]. The proposed mechanism for propane-1,2-diol hydrogenolysis is limited by the availability of hydrogen for acetol hy­
formation on Ni− Cu/Al2O3 catalyst entails the adsorption of glycerol drogenation (see Fig. 2 for mechanism details). Essentially, the
onto an acid site of Al2O3 oxide through its central hydroxyl, which loses reforming of glycerol towards hydrogen limits propane-1,2-diol forma­
tion, leading to an increase in acetol yields when glycerol reforming
decreases [37]. When Ni− Cu is supported on MgO, the reaction mech­
Table 3
anism shifts from an acid route (acetol intermediary) to a basic route,
Most relevant details for the propane-1,2-diol production from glycerol on
Ni− Cu based catalysts.
resulting in the production of up to 50 % lactic acid [37]. Lactic acid is
also produced on Ni− Cu/NaY(zeolite) following the basic route, but
Catalyst Glycerol conversion/ Hydrogen donor or Reference
propane-1,2-diol selectivity reaches a value of 31.8 % with a glycerol
Propane-1,2-diol external H2 source
selectivity conversion of 96.4 % [38]. Ethanol and acetol are also detected on
Ni− Cu/NaY(zeolite) catalyst when the basic route occurs [38]. There­
Ni− Cu/TiO2 100% / 89.7% (at 230 Propane-2-ol [30]
◦
C)
fore, the mechanism followed during the glycerol conversion towards
Ni− Cu/Al2O3 90% / 82% (at 220 ◦ C) Formic acid [31− 33] propane-1,2-diol is conditioned by the supports employed and the
Ni− Cu/ZnO/ 87.1% / 85.5% (at 220 Methanol [34] availability of basic or acid sites on them.
Al2O3 ◦
C)
Ni− Cu/ZnO/ 82.0% / 86.7% (at 220 Propane-2-ol [35]
2.2.2. External hydrogen supply: mechanism and performance optimization
Al2O3 ◦
C)
Ni− Cu/Al2O3 80% / 25% (at 250 ◦ C) Despite the challenges associated with the use of an external
Ni− Cu/ZSM-5 85% / 25% (at 250 ◦ C) Glycerol itself [36] hydrogen source and its associated costs, the glycerol conversion and
(zeolite) selectivity toward propane-1,2-diol are considerably higher compared
Ni− Cu/Al2O3 90% / 50% (at 250 ◦ C) H2 supplied [36] to using in situ generated hydrogen. For instance, on the Ni− Cu/Al2O3
externally
Ni− Cu/30 % 80% / 25% (at 250 ◦ C) Glycerol itself [37]
catalyst with external hydrogen, the glycerol conversion reaches
MgO-Al2O3 approximately 90 %, with a selectivity toward propane-1,2-diol of 50 %.
Ni− Cu/NaY 96.4% / 31.8% (at 260 Glycerol itself [38] This selectivity is double than that achieved when using hydrogen
(zeolite) ◦
C) generated in situ from glycerol on the same catalyst [36]. Additionally,
Ni− Cu/Al2O3 > 71.6% /88% to 98 % H2 supplied [41− 46]
the reactivity of the Ni− Cu/Al2O3 catalyst can be modulated to produce
externally
Ni− Cu(3 %)/SiO2 100% / 92% (at 220 ◦ C) H2 supplied [39] propane-1,2-diol with a selectivity ranging from 88 % to 98 % using
externally external hydrogen [41–46].
Ni− Cu/M-SAPO- 90.2% / 100% (at 240 H2 supplied [40] Moreover, complete glycerol conversion and a propane-1,2-diol
11(zeolite) ◦
C) externally selectivity of 92 % is achieved using the Ni− Cu(3 %)/SiO2 catalyst
Ni− Cu/ 32.11% / 94% (at 200 H2 supplied [47]
Al2O3–CuCr ◦
C) externally
during the vapor phase hydrogenolysis of glycerol at 220 ◦ C and 30 bar
Ni− Cu/AC(active 97.5% / 87.3% (at 220 H2 supplied [48] pressure [39]. Similarly, a selectivity close to 100 % is attained with
carbon) ◦
C) externally Ni− Cu supported on M-SAPO-11 zeolite at 240 ◦ C [40]. The modified
Ni− Cu/SiO2 95% / 90% (at 200 ◦ C) H2 supplied [49] structure of M-SAPO-11 zeolite facilitates the diffusion of reactants
externally
compared to conventional SAPO-11 zeolite, whereas the addition of Ni

8
J.L.C. Fajín and M.NatáliaD.S. Cordeiro Molecular Catalysis 561 (2024) 114168

promotes the formation of highly dispersed metallic nanoparticles, of these chemicals on Ni− Cu/γ-Al2O3 catalysts [50]. Besides the selec­
contributing both along with a superior metal-acid synergic effect to the tivity of Ni− Cu/γ-Al2O3 catalysts can be can be shifted from propane to
high reactivity of this catalyst [40]. In fact, only traces of byproducts as CO2 by combining, in equal proportion, this catalyst with another one
acetol or ethylene glycol are obtained using the Ni− Cu/M-SAPO-11 based on Pt/C. This process allows for the effective gasification of
catalyst, showing its ability to block side reactions effectively [40]. glycerol at 350 ◦ C [51].
Other catalysts that demonstrate noteworthy glycerol conversion Instead, glycerol derivatives can be produced through electro­
and selectivity toward propane-1,2-diol when supplied with externally chemical oxidation, as exemplified by the formation of formate at the
provided hydrogen include Ni− Cu/Al2O3–CuCr, reaching a maximum cell anode, subsequently yielding formic acid. Simultaneously, ammo­
selectivity of 94 % [47], Ni− Cu/AC(AC: active carbon), exhibiting a nium is produced through cathodic reduction of nitrate. Both cell elec­
selectivity of 87.3 % [48], and Ni− Cu/SiO2 with a selectivity of 90 % trodes employ catalysts based on NiCu-OH, operating under a low cell
[49]. Propane-1,2-diol is formed in the latter catalysts through an acetol potential of 1.37 V at a current density of 100 mA cm‒2 [52]. Alterna­
intermediary under acid conditions [48,49]. tively, formic acid can also be obtained through glycerol electro­
Therefore, the use of hydrogen donors in the hydrogenolysis of oxidation using Ni− Cu supported on an active carbon felt (ACF) as a
glycerol over Ni− Cu catalysts is very convenient due to the high- catalyst [53]. The most reactive catalyst (Ni1Cu1@ACF) achieves a
pressure requirement for externally supplied hydrogen, but the activ­ selectivity toward formic acid of up to 97.4 %. This selectivity is
ity and selectivity obtained when using the first option are considerably attributed to the excellent conductivity, chemical inertness, and porous
lower than when the reaction is carried out using externally supplied structure of the active carbon felt, along with the catalytic properties of
hydrogen bimetallic Ni− Cu nanoparticles [53].
Furthermore, glycerol electrooxidation under alkaline conditions on
Ni− Cu modified carbon ceramic electrodes drives to the formation of
2.3. Formation of other products from glycerol organic acids such as oxylic, glycolic, glyoxylic, formic, etc. [54] This
electrooxidation process involves the transformation of 1,3-dihydroxy­
As previously mentioned, glycerol conversion not only produces acetone to hydroxypyruvic acid, which is then converted to ketoma­
desirable products but also yields valuable byproducts. By carefully lonic acid, ultimately producing oxalic, glycolic, and glyoxylic acids.
modulating the structure of Ni− Cu catalysts and adjusting reaction Alternatively, glycerol electrooxidation can progress through the glyc­
conditions, it becomes possible to boost the formation of some of these eric acid intermediary, which is converted to tartronic acid and further
byproducts. Therefore, Ni− Cu catalysts hold the advantage of easy to ketomalic acid. Glyceric acid can also produce formic and glycolic
modulation to generate the desired product during the glycerol con­ acid, with the latter evolving into oxalic acid.
version, in addition to their lower cost and improved thermal stability. In summary, a diverse array of valuable products can be obtained
Details about the formation of these byproducts can be seen in Table 4. from glycerol using Ni− Cu based catalysts by adjusting the catalyst
For example, glycerol can be decomposed into methanol, generating structure and composition, as well as the reaction conditions.
additional H2 through methanol steam reforming (refer to the scheme in
Fig. 2 for mechanism details) [28,63]. Besides lactic acid, with a selec­ 3. Conclusions and outlook
tivity of up to 50 %, is produced in Ni-Cu/MgO catalysts where the basic
route is followed [37]. This work provides a comprehensive summary and discussion of the
Moreover, Ni− Cu/γ-Al2O3 catalysts with different Ni/Cu ratios were significant advancements in glycerol conversion to valuable products
prepared for use in the gas-phase glycerol conversion to valuable using Ni-Cu based catalysts. This process is particularly advantageous
products [50]. The gradual incorporation of Cu to the catalyst surface due to the increasing availability of glycerol, a byproduct of biodiesel
reduces the formation of CH4, which it is obtained through a deep production, which aligns with the growing production of biodiesel.
hydrogenolysis of glycerol [50]. This suggests that glycerol hydro­ Besides the valorization of this byproduct not only enhances the sus­
genolysis towards methane requires sites with adjacent Ni atoms, which tainability of biodiesel production but also adds significant value to the
become less abundant as the Cu concentration on the surface increases process.
[50]. The progressive increase in Cu content shifts the catalyst’s selec­ Glycerol can undergo various catalytic reactions, including reform­
tivity from methane towards dehydration and dehydrogenation prod­ ing, hydrogenolysis, dehydration, electrooxidation, or hydrogenation,
ucts such as hydroxyacetone, pyruvaldehyde, lactide, and/or pyruvic resulting in a wide range of valuable chemicals such as hydrogen, pro­
acid. Pyruvaldehyde is formed through hydroxyacetone dehydrogena­ pylene glycol (propane-1,2-diol), propane-1,3-diol, lactide, acrolein,
tion, and it can further generate lactic acid or pyruvic acid, and lactide dihydroxyacetone, pyruvaldehyde, acetaldehyde, ethylene glycol,
through lactic acid dimerization [50]. Hydroxyacetone hydrogenation glyceraldehyde, lactic acid, acetic acid, formic acid, pyruvic acid,
can also lead to propane-1,2-diol or acetaldehyde plus formaldehyde, glyceric acid, tartronic acid, oxylic acid, glycolic acid, and glyoxylic
from which acetic acid and formic acid can be obtained [50]. Thus, acid, among others.
adjusting the Ni/Cu ratio can induce a high-proportion formation of one The work demonstrates the potential to overcome limitations asso­
ciated with conventional catalysts commonly used in these reactions,
Table 4 including low activity, selectivity, stability, or high cost, by employing
Details for the formation of different byproducts during the glycerol decompo­ inexpensive Ni‒Cu-based catalysts. These catalysts also benefit from the
sition on Ni− Cu based catalysts. abundance of their components and high thermal stability conferred by
Chemical Catalyst/s Selectivity /reaction References the formation of the alloy. Indeed, the activity and selectivity of these
conditions catalysts can be precisely modified to achieve the desired products. The
Lactic acid Ni− Cu/MgO 50% / 250◦ ; 40 bar [37] versatility of these catalysts opens avenues for producing a spectrum of
Cu/γ-Al2O3 2.77% / 300◦ ; 1013 bar [50] chemicals crucial for a wide array of industrial applications. Besides the
Methane Ni/γ-Al2O3 100% / 300◦ ; 1013 bar [50] valorization of glycerol through advanced catalytic reactions aligns
Hydroxyacetone Ni− Cu12/γ-Al2O3 34.5% / 300◦ ; 1013 bar [50]
seamlessly with the overarching goal of achieving sustainable and eco-
Pyruvaldehyde Ni− Cu12/γ-Al2O3 17.6% / 300◦ ; 1013 bar [50]
Lactide Ni− Cu18/γ-Al2O3 51.1% / 300◦ ; 1013 bar [50] friendly biodiesel production. By converting a byproduct into valuable
Pyruvic acid Ni− Cu18/γ-Al2O3 4.05% / 300◦ ; 1013 bar [50] chemicals, we not only mitigate waste but also contribute to a more
Acetic acid Ni− Cu21/γ-Al2O3 3.41% / 300◦ ; 1013 bar [50] sustainable and circular approach in the biofuel industry.
Formic acid Ni1Cu1@ACF 97.4% /current density of [53] Special attention is paid to glycerol reforming for hydrogen pro­
(Active carbon felt) 1.31 mA cm− 2 at 1.895 V.
duction, where the water gas shift reaction and methanol steam

9
J.L.C. Fajín and M.NatáliaD.S. Cordeiro Molecular Catalysis 561 (2024) 114168

reforming processes play a crucial role. Reaction mechanisms for glyc­ Declaration of competing interest
erol reforming on Ni− Cu catalysts are discussed, outlining their most
plausible reaction routes. Understanding the reaction mechanisms on The authors declare that they have no known competing financial
Ni–Cu catalysts provides a roadmap for optimizing hydrogen generation interests or personal relationships that could have appeared to influence
processes, crucial for various industrial applications. Concretely, it is the work reported in this paper.
explained that Ni–Cu catalysts favor the formation of CO2 and H2 though
the preferential decomposition of glycerol toward methanol, whose Data availability
subsequent reforming toward CO and H2 and the CO oxidation by WGS
reaction are also favored on Ni− Cu catalysts. Importantly, this bime­ No data was used for the research described in the article.
tallic combination blocks side reactions leading to the formation of coke
which poisons the reforming catalyst or methane which consumes
hydrogen. Moreover, the use of CO2 sorbents, such as CaO contributes to Acknowledgments
almost CO-free hydrogen yield which it is very convenient to its further
use in FC. This work received support and help from FCT/MCTES (LA/P/0008/
An optimum temperature to carried out the glycerol reforming of 2020 DOI 10.54499/LA/P/0008/2020, UIDP/50006/2020 DOI
225 ◦ C was obtained on several Ni− Cu catalysts which encompasses a 10.54499/UIDP/50006/2020 and UIDB/50006/2020 DOI 10.54499/
high glycerol conversion with a high activity for the WGS reaction. The UIDB/50006/2020), through national funds. JLCF thanks FCT for
generalization of this achievement is limited by the low number of funding into framework of Norma Transitória - DL 57/2016/CP1346/
catalysts tested. Therefore, future investigations should explore the 001.
impact of temperature on glycerol reforming with other catalysts, as
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