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Current Opinion in Green and Sustainable Chemistry xxx (2016) 1e4

Contents lists available at ScienceDirect

Current Opinion in Green and Sustainable Chemistry

journal homepage: http://www.journals.elsevier.com/current-opinion-ingreen-and-sustainable-chemistry/

Review article
Q1,3

Benign-by-design catalysts and processes for biomass conversion*

Q2

Rafael Luque
Departmento de Quimica Organica, Universidad de Cordoba, Campus de Rabanales, Ed. Marie Curie (C-3), Ctra Nnal IV-A, Km 306, E14014, Cordoba, Spain

a r t i c l e i n f o
Article history:
Received 13 July 2016
Received in revised form
16 September 2016
Accepted 20 September 2016
Available online xxx

The design of catalytically active nanomaterials with improved

activity and stability for biomass conversion has become a hot topic
in recent years in view of the transition towards a bio-based
economy [1e6]. Nanomaterials indeed became a hot topic in
recent years due to the unique and most outstanding properties of
such nanoentities that include large surface to volume ratio areas
(as compared to bulk metals), degenerated density of energy stages
and unprecedented selectivities and specicities due to the possibility to optimise particle geometry (size and shapes) for specic
reactions [7e9].
A number of key examples largely illustrate nowadays the potential of catalysts design based on fundamental understanding for
a more sustainable chemical industry (Fig. 1) [10,11]. One of the
most relevant features of catalytic systems for biomass conversion
relates to their stability under typical biomass processing conditions. These include moderate to high temperatures and pressures
and most importantly the presence of water. Recent developments
in the eld provided efcient and highly promising approaches
towards highly active and stable catalysts controlling both support
nanoarchitectures for nanoscale metal trapping as well as high
loaded atomically dispersed metals on porous materials which
exhibited excelling catalytic activities and stabilities in heterogeneously catalyzed processes [12e18].
Single-atom site nanocatalysts indeed possess excellent prospects in biomass conversion. In addition to their reported high
catalytic activities and stabilities, the possibility to diversify in
terms of metal (e.g. noble vs non noble) and supports provides
single atom sites nanomaterials with attractive tuneabilities for a
range of processes. Remarkable recent examples paved the way to

*
Dedicated to Prof. James H. Clark, mentor, colleague and friend, on the occasion
of his 65th anniversary.
E-mail address: q62alsor@uco.es.

the design of Pt and bimetallic (PtRu) based systems designed from

fundamental understanding on various principles.
Stable Pt1 single atom systems containing high Pt loadings (ca.
1 wt%) could be prepared on phosphomolybdic acid(PMA)modied active carbon by stabilizing Pt atoms on four oxygens
from the four-fold hollow sites on PMA (Scheme 1) [12]. Importantly, the anchored Pt atoms strongly interact with the PMA
carbonaceous support which may provide a superior stability of the
catalyst in heterogeneous catalyzed processes (e.g. biomass conversion). Based on the designed system, positively charged Pt atoms
in fact exhibited an excellent performance in the hydrogenation of
nitrobenzene and cyclohexanone [12], with a signicant potential
to be further extended to the hydroconversion of biomass-derived
compounds as well as to a range of high loading single-atom catalysts combining other metals and supports which certainly the
authors will report in due course.
Similar systems based on carbon-supported Ti0.1W0.9C nanoparticles coated with Pt or bimetallic PtRu monolayers have also
been recently reported to be designed by carburizing mixtures of
noble metal salts and transition metal oxides encapsulated in
removable silica templates [13]. Atomically thin noble metal
monolayers could then coat the transition metal carbide nanoparticles to provide an elegant and highly controllable core-shell
architecture in terms of particle size, monolayer coverage and
heterometallic composition. The most attractive features of the
proposed advanced catalytic system relate to an improved resistance to sintering and CO poisoning, being potentially useful for
CH4/CO2 conversion in mixtures containing CO. These nanocatalytic
systems were employed in methanol electrooxidation, with
remarkably observed improved specic activities (an order of
magnitude higher) to those of commercial catalysts after 10,000
cycles [13].
Additionally, benign-by design nanocatalysts can also avoid the
over-utilization of precious metals (e.g. Pt) with a remarkable efciency for clean industries. An elegant atom-trapping technique
was devised to similarly stabilize Pt atoms onto nanoscaled ceria
supports with various forms and shapes acting as nanoscale trap
[14]. Such stabilization prevented Pt agglomeration and sintering
under high temperatures (up to 800  C) and various harsh reaction
conditions, hence avoiding the use of large loadings of noble metals
in heterogeneous catalyzed processes. These ndings constitute
another signicant advance towards future designs of increasingly

http://dx.doi.org/10.1016/j.cogsc.2016.09.004
2452-2236/ 2016 Published by Elsevier B.V.

Please cite this article in press as: R. Luque, Benign-by-design catalysts and processes for biomass conversion, Current Opinion in Green and
Sustainable Chemistry (2016), http://dx.doi.org/10.1016/j.cogsc.2016.09.004

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R. Luque / Current Opinion in Green and Sustainable Chemistry xxx (2016) 1e4

Fig. 1. Benign-by-design catalysts and processes for a more sustainable future.

Scheme 1. Design of Pt single atoms on PMA-modied activated carbon, with most

stable conguration based on DFT calculations. Copyright Wiley-VCH Verlag. Reproduced with permission from reference [12].

stable and environmentally sound catalytic systems in industrial

chemical processes.
In line with the design of the proposed benign-by-design catalytic systems, the replacement of all above discussed noble metals
with cheaper and more environmentally friendly transition metal
catalysts (e.g. Fe and/or related metal carbide/nitride systems) still
remains a signicant challenge. As example to illustrate this point,
carbon supported FeNi nanoparticles were designed using a simple
carbothermal reduction of cellulose lter paper impregnated with
Fe and Ni salts as replacement of typical noble metals (Pd, Pt)
employed in hydrogenation reactions [15]. The proposed transition
metal bimetallic system was successfully employed in the continuous hydrogenation of biomass-derived platform chemicals
including C6 and C5 sugars (glucose and xylose), furanics and derivatives (HMF and levulinic acid) as well as a range of carbonyl and
double-bond containing chemicals at moderate temperatures (50150  C) and hydrogen pressures [15]. The most attractive features of
the proposed systems relate to their high stability (over 80 h, time

on stream) over a wide range of conditions as well as scaled-up

experiments of up to ve-fold increase in the reagent concentration (e.g. glucose) with quantitative yields still obtained under
those conditions.
Based on these highlighted examples, new directions are provided to the benign-by-design preparation of advanced catalytic
systems based on fundamental understanding aiming to 1) reduce
metal loadings, 2) enhance catalytic activity, 3) increase the stability of metal catalysts and 4) potentially replacing expensive and
environmentally unfriendly noble metals by transition metal catalysts (e.g. Fe).
In addition to these relevant steps towards benign-by-design
systems with a signicant potential for biomass conversion (not
explored to date), there are related relevant examples of similarly
designed active and stable systems for biomass conversion.
Focusing on a particular example (lactic acid, LA) to illustrate
this potential, Ag-based catalytic systems were recently reported as
highly active and selective for lactic acid production from glycerol
under mild reaction conditions. The chemical production of lactic
acid can offer a signicant advantage to the extensively established
and well known bioconversion process in terms of an improved
productivity (as compared to the limited productivity of sugar
fermentation) and the avoidance of large quantities of generated
gypsum (1 ton per ton of LA) [16].
The most investigated alternative chemical process is the
aqueous-phase isomerisation of 1,3-dihydroxyacetone (DHA)
catalyzed by Lewis acid systems [17,18]. With this purpose, an
innovative chemo-enzymatic approach was proposed based on the
enzymatic oxidation of glycerol (GLY) to 1,3-dihydroxiacetone
(DHA) followed by a Lewis-acid catalysed isomerisation in water
or in methanol via an alkyl lactate (AL) intermediate using highly
active, selective and recyclable tin-containing MFI zeolites prepared by scalable methods (Scheme 2) [19].
These outstanding results by the group of Perez-Ramirez were
also supported by life cycle analysis of a process comprising the
enzymatic production of dihydroxyacetone from crude glycerol and
its chemocatalytic isomerisation in methanol shown as advantageous for the production of lactic acid as compared to glucose
fermentation from both sustainability (energy requirements and
CO2 emissions) and operating/economic standpoints [19]. The bio-/
chemocatalytic route remained environmentally and economically
more attractive even if the purity of glycerol was as low as 38%,
illustrating the remarkable potential of the benign-by-design (bio)
catalytic systems and processes for biomass conversion towards a
future bioeconomy.
More recently, the same group developed an alternative strategy
utilizing designed Ag/Al2O3 catalysts in combination with the
previously reported tin-containing MFI zeolites [20] for a fully
chemocatalyzed two step one-pot process conversion of GLY to
pyruvaldehyde (PAl) via oxidehydration on Ag/Al2O3 (80% yield,
350  C and O2/GLY 0.5 ratio) followed by continuous ow Lewis
acid isomerization into LA and methyl lactate at 70  C over the
aforementioned Sn-containing zeolites [20]. Remarkably, the proposed chemocatalytic system was highly stable, particularly the
isomerization step.
A further conversion of lactic acid into lactide and polylactic
acid-type polymers was also possible, as recently demonstrated by
the group of Sels [21]. With the possibility to derive lactic acid from
biomass/waste feedstocks illustrated above, a similar zeolite system (H-Beta) to that previously reported for LA conversion from
DHA or PAl [19,20] was reported to be highly selective for lactide
synthesis (ca. 79% yield at full LA conversion) in the conversion of
nsted acid-catalysed
concentrated aqueous LA solutions via Bro
condensation of two LA molecules followed by dehydration to
L,L-lactide (Scheme 3). The simple and highly efcient direct lactide

Please cite this article in press as: R. Luque, Benign-by-design catalysts and processes for biomass conversion, Current Opinion in Green and
Sustainable Chemistry (2016), http://dx.doi.org/10.1016/j.cogsc.2016.09.004

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R. Luque / Current Opinion in Green and Sustainable Chemistry xxx (2016) 1e4

Scheme 2. Conventional LA production via glucose (GLU) fermentation versus an alternative bio-chemocatalytic approach based on the enzymatic oxidation of glycerol (GLY) to 1,3dihydroxiacetone (DHA) followed by isomerization in water or in methanol via an alkyl lactate (AL) intermediate. Reproduced by permission of the Royal Society of Chemistry from
ref. [19].

Scheme 3. Current process for lactide synthesis and subsequent polymerization (left, red box) as compared to the proposed alternative zeolite-catalysed process (right, blue box).
Reproduced with permission from reference [21]. (For interpretation of the references to colour in this gure legend, the reader is referred to the web version of this article.)

Please cite this article in press as: R. Luque, Benign-by-design catalysts and processes for biomass conversion, Current Opinion in Green and
Sustainable Chemistry (2016), http://dx.doi.org/10.1016/j.cogsc.2016.09.004

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synthesis was proposed as alternative to the traditional two-step

industrial process involving a hardly controllable polycondensation step followed by backbiting, with a signicant
complexity and low yields of pure lactide together with a signicant formation of side products. Based on these premises, the authors further proposed a fully scalable process concept in which the
zeolite-catalysed lactide production could be conducted in a stirred
tank reactor (R1) with continuous water removal (from the dehydration step lactide) with a yield of 85% in toluene, followed by
further purication (up to 98% pure, batch extraction) [21]. The
process is additionally exible in the amount of water initially
present in the feed, making it potentially compatible with dilute
fermentative LA mixtures. The selected catalyst, apart from being
highly active, stable and cheap (currently utilized in petroleum
rening), was also found to be highly stable under the investigated
reaction conditions in the proposed organic media (o-xylene, 6
consecutive runs) with a full activity and selectivity regeneration
possible after each run via calcination.
The proposed contribution has been provided to illustrate, with
selected top literature examples, the existing possibilities of benignby-design rational synthesis of (nano)catalysts and processes with a
particular emphasis on activity and stability enhancement in view
of their utilization in biomass conversion. The example of lactic acid
(production and subsequent conversion to lactide and PLA) exemplies the potential of such processes and technologies as
replacement of existing petroleum-derived approaches and will
pave the way to further developments in the eld being the way
forward to a more sustainable society and future bio-based
industries.

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Acknowledgments
Rafael Luque gratefully acknowledges Consejeria de Ciencia e
Innovacion, Junta de Andalucia for funding project P10-FQM-6711
as well as funding from H2020 program under projects ITN Photo4Future (H2020-MSCA-ITN-2014-641861), HUGS (H2020-MSCAITN-2015-600825) and COSMIC (H2020-MSCA-ITN-2016-721290).

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Please cite this article in press as: R. Luque, Benign-by-design catalysts and processes for biomass conversion, Current Opinion in Green and
Sustainable Chemistry (2016), http://dx.doi.org/10.1016/j.cogsc.2016.09.004

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