Nanocatalysis For Green Chemistry

Definition of the Subject
Nanocatalysis for Green

Chemistry Nanocatalysis is a new Green Chemistry era. The
continuous increase of recalcitrant pollutants in
Layla Filiciotto and Rafael Luque the environment calls for the sustainable develop-
Departamento de Química Orgánica, Universidad ment of the chemical industry. Nanocatalysis has
de Córdoba, Córdoba, Spain the potential to improve substantially a variety of
chemical processes by minimizing energy and
feedstock requirements. Most of all, nanocatalysis
fulfills all the Green Chemistry principles,
Article Outline allowing the development of truly sustainable
processes.
Glossary
Definition of the Subject
Introduction Introduction
Catalysis
Nanocatalysis The current environmental and organizational
Noble Metal Nanoparticles: Gold and Palladium global challenges comprising
Nonnoble Metal: Iron/Iron Oxide Nanoparticles
Transition Metal Oxide Nanoparticles • Climate change mitigation
Organic Nanoparticles: Carbon • Depletion of traditional feedstocks (i.e.,
Future Directions petroleum)
References • Intensification of the world-wide population
density (hence, continuous increase of energy
Glossary and food demands)
Catalysis Increase of the reaction rate by means call for the development of new technologies and
of an additional organic/inorganic/hybrid sub- materials, as well as the evolution towards a new
stance called catalyst, which remains unaltered mental age where sustainability, durability,
during the course of the reaction. recycling, cost-effectiveness, and conservation of
Green Chemistry Philosophy focused on the limited resources are part of a person’s daily life.
design, development, and implementation of Anthropological development in the past centu-
environmentally friendly, harmless, and eco- ries has seen an incredible technology boom,
nomical chemical processes. improving the quality of life of a substantial part of
Nanocatalysis Enhancement of the reaction rate the world population. The particular development of
by means of a solid substance of nanometer coal-fired steam engines marked the first Industrial
dimensions. Revolution of the eighteenth century. At that time,
Nanoparticle Organic/inorganic/hybrid material the world saw a shift from less efficient renewable
of nanoscale dimensions. resources (e.g., wood for heat and energy, water
Sustainability Ability to implement and perpet- wheels/wind mills as early turbines) to fossil fuels,
uate industrial and social practices with the opening incommensurable possibilities in the chem-
protection of the environment as a focus. ical, energy, and transportation industries. Later in
mid-nineteenth century, the first rock oil well was
drilled, and the petroleum era begun. Kerosene was
the first commercial oil-based product, substituting
# Springer Science+Business Media, LLC, part of Springer Nature 2018 1
R. A. Meyers (ed.), Encyclopedia of Sustainability Science and Technology,
https://doi.org/10.1007/978-1-4939-2493-6_1007-1
2 Nanocatalysis for Green Chemistry
whale oil and wood for illumination and heating, was able to trigger people’s awareness on the
respectively. The rapid technological improvement harmful effect of pesticides on local ecosystems
in oil wells exploration made petroleum the major (in particular, persistent organic pollutant, DDT),
source of commodity chemicals, materials, and affecting different environmental compartments
fuels. For instance, synthetic petroleum-based plas- (i.e., water, sediments, and biota). Silent Spring
tics promptly flourished in the early 1900s, first with became the first hallmark of the modern environ-
the advent of Bakelite (1907), followed by polysty- mental movement for both the public and scien-
rene (1929), polyester (1930), polyvinylchloride tific community. Chemicals started to be under
(1933), and nylon (1935) [1]. Plastics became inte- scrutiny in terms of unwanted effects on human
grative part of the ordinary life of the average per- and animal health, soil, ground water, and
son, starting the concept of disposable objects and atmosphere.
the deleterious throwaway-culture. The petroleum The increase of awareness in the beginning of
industries at that time seemed self-perpetuating, and the 1960s on the anthropological effect on Earth’s
impacts on the environment were overlooked. ecosystems has moved political agendas to the
The exceptional broad success of plastics has implementation of new legislations protecting
not gone unnoticed. Nowadays, microplastic pol- the environment, such as the 1969 US National
lution is ubiquitous. Microsized plastic materials Environmental Policy Act (NEPA). This act was
were found in freshwaters, seas, and even fish aimed to enforce the Environmental Assessments
[2]. As a curious fact, the average European shell- (EAs) and Environmental Impact Statements
fish eater would consume 11,000 microplastics (EISs) prior to undertaking any major federal
per year [3]. Additionally, the recent break of action (e.g., airports, military complexes) that
record of continuously increasing atmospheric would affect negatively the environment. Shortly
CO2 [4] level calls for the development of truly after, former US president Richard Nixon insti-
sustainable processes and the full embrace of the tuted the Environmental Protection Agency (EPA)
Green Chemistry concept. whose regulations have played a significant role in
Sustainability is a joint global effort, where the prevention of anthropological pollution. For
science covers a special role. Thanks to talented instance, EPA’s first action was to ban the use of
scientists, renewable, harmless, nontoxic pro- DDT, along other chemical pesticides. Finally the
cesses can be achieved. In particular, catalytic dangers of chemicals were understood, and the
processes can improve greatly the sustainability scientific community had the role of finding the
of a process, as well as reduce the amount of solutions to irreversible human-induced changes
energy and feedstock needed for an industrial to the environment. International treaties started to
manufacture. As a result, this chapter aims to be implemented, such as the Montreal Protocol
contribute on the role of catalysis in green chem- (1987), which aimed to ban ozone-depleting sub-
istry. An overview on the main principles and stances based on the work of talented researchers
concepts of green chemistry and catalysis will be of the time (a few names: Mario Molina, Frank
given. In particular, the bridge between homoge- Sherwood Rowland, Paul J. Crutzen–Nobel Prize
neous and heterogeneous catalysis, nanocatalysis, for Chemistry 1995), reducing dramatically the
will be discussed. A particular focus to sustainable number of emitted atmospheric pollutants
catalytic nanomaterials will be given in honor of [5]. The Montreal Protocol proves that sustain-
the 12 Principles of Green Chemistry. ability is only achieved as a joint global effort:
the ozone layer hole over the South Pole is pre-
Green Chemistry dicted to close permanently by 2050 [6].
In 1962, American marine biologist Rachel Car- Although bans and remediation of contami-
son published Silent Spring, a book that would nated areas were the original priority of the envi-
change the general view on chemicals and their ronmental agencies of the time, the idea of
detrimental effect on humans and the environ- pollution prevention consequently started to
ment. With her groundbreaking book, Carson develop among environmentalists, culminating
Nanocatalysis for Green Chemistry 3
in the establishment of the Office of Pollution conducted at room temperature and atmo-
Prevention and Toxics within the EPA in 1988 spheric pressure. Not only this has positive
and of the Pollution Prevention Act of 1990. Con- economic impacts, but also the environment
cepts such as benign-by-designs [7], green chem- greatly benefits from reducing the energy
istry [8], E-factor [9], and atom economy [10] requirements (mainly fossil-based).
began to be developed, marking the beginning of 7. Use of Renewable Feedstocks: When a non-
a new philosophy among the researches. In the renewable feedstock/raw material is used, a
interim, the scientific journal Green Chemistry future where that chemical process is
was brought forth by Prof. James Clark unfeasible shall be imagined. Renewable
(University of York), giving a tangible platform feedstocks will allow the ever endurance of
to motivated academic and industrial scientists. the process.
With the revolutionary book Green Chemistry: 8. Reduce Derivatives: Every added step in a
Theory and Practice written by Anastas and War- chemical process generates waste. The trans-
ner [11], a new doctrine was born in the scientific formation of a chemical product into its deriv-
community based on the reduction and/or elimi- ative by the use of blocking groups for
nation of hazardous substances (i.e., risk and haz- protection/deprotection and/or temporary
ards) in each step of a chemical synthesis, as well modification of physical/chemical processes
as minimization of wasteful practices, reducing applications should be avoided or minimized
costs, energy, and materials employed. In partic- if necessary.
ular, the book proposed the now famous 12 prin- 9. Catalysis: If a chemical process can be car-
ciples of Green Chemistry, being: ried out with a catalyst instead of a reagent,
thus it shall be implemented.
1. Prevention: Waste is unnecessary. Preven- 10. Design for (Bio)Degradation: Chemical
tion of waste shall be preferred to its subse- products shall be designed to degrade in the
quent disposal/treatment. safest way for human, animal, and environ-
2. Atom Economy: Chemical processes shall ment. End-of-life products should preferably
be designed to be as efficient as possible: all be biodegradable, if not, be degraded into
the atoms used as reagents should be incor- harmless compounds.
porated in the final product. 11. Real-time analysis for Pollution Preven-
3. Less Hazardous Chemical Syntheses: tion: Only with the understanding of each
A chemical process shall be designed to chemical step a process can be designed to
incorporate and/or produce the least or zero be as safe as possible. In situ/real-time ana-
substances that might have a harmful impact lytical methods need to be developed to con-
on humans, animals, and the environment. trol in advance the possible formation of
4. Designing Safer Chemicals: The product of hazardous substances.
a new chemical process shall be designed to 12. Inherently Safer Chemistry for Accident
have the best properties for their application, Prevention: Leakages of dangerous
but most importantly should not possess any chemicals to the environment, explosions,
toxic/noxious/deadly properties. and fires must be null. Careful design of the
5. Safer Solvents and Auxiliaries: A chemical process and substances used can prevent haz-
process shall involve the least amount of ards, casualties, and environmental
“spectator substances”: solvents, separating/ imbalances.
drying agents, surfactants, stabilizers, visco-
sifiers, etc. that are not strictly necessary for Conceptually, the whole list of principles of
the function of the product. If inevitable, the Green Chemistry can be summarized in one
substance shall be harmless. word: design. In fact, prevention and minimiza-
6. Design for Energy Efficiency: The abso- tion of risks and hazards for the environment,
lutely energy efficient process is when production costs (in terms of operating conditions,
atom economy, auxiliary substances), and waste 3. Reaction on the catalytic active site
generation (reagents in excess, non-selective pro- 4. Desorption/Elimination of the product from
cesses) can be achieved through careful process/ the catalytic active site
product design (and re-design, if unsuccessful or 5. Diffusion of the product to its collection point
with a margin of improvement). Being a Green
Chemist is to consider in advance the environ- In particular, the adsorption or coordination of
mental issues of a particular process and dedicate a compound on a catalytic surface or metal center
the efforts into carrying out the chemical steps can drastically lower the required energy for the
with the 12 principles in mind, where one does reaction completion. In fact, a catalytic process in
not exclude the other. In fact, the list of principles kinetic regime may allow overcoming thermody-
is meant to be a cohesive system of design [12], as namic limitations of unfavorable reactions by
a truly sustainable process is achieved when increasing the reaction rate. For instance, olefin
all the green chemistry requirements are metathesis would have been unfeasible without
implemented. the development of transition-metal based cataly-
Peculiarly, catalysis (9th principle) fulfills sis which awarded Chauvin, Grubbs, and Schrock
most of the Green Chemistry requirements, as the Nobel Prize in Chemistry in 2005 [14].
the use of a catalyst has been proven more selec- A catalytic system is classified as homoge-
tive (minimization of waste and improvement of neous if in the same phase as the reactants (e.g.,
atom economy) and safer (prevention of risks). soluble metal complexes) and heterogeneous if
Furthermore, catalysis is able to reduce overall immiscible with the reactants (e.g., metal oxides)
production costs by reducing energy requirements (Fig. 1). Homogeneous catalysis often allows the
for a given reaction. Also, catalysis has the poten- same reaction to be carried out with higher selec-
tial of allowing (unfavorable) reactions to take tivities at lower operating conditions compared to
place with greener solvents and conditions. heterogeneous systems, however presenting
drawbacks in terms of catalyst separation and
reuse. Common industrial practices include at
Catalysis least one catalytic step with either a homogeneous
or heterogeneous catalyst, accounting for ca. 90%
One of the pillars of Green Chemistry, catalysis, of all chemical production [15] thanks to its
demonstrated to be the optimum ally for many energy, feedstocks, and waste-related benefits.
chemical syntheses, as well as making the impos- Importantly, catalysis has covered a key role in
sible possible. the advancement of green chemistry practices. For
The term catalysis was first coined by Jacob instance, challenging selective oxidations or
Berzelius (1835) [13] in the attempt to describe reductions were traditionally carried out with haz-
the acceleration phenomena given by certain sub- ardous stoichiometric reagents (e.g., permanga-
stances that remain unchanged after a reaction, nates, chromates, and metal hydrides), producing
exercising an “action very different from chemical copious amounts of waste (i.e., inorganic salts)
affinity.” De facto, a catalyst is a material or sub- [16]. The use of recyclable solid acids and bases
stance with the action (ability) of lowering the in juxtaposition with green reagents (e.g., molec-
activation energy of a given reaction without ular oxygen, hydrogen peroxide, and hydrogen)
being consumed, resulting in faster and/or more can substitute efficiently classical stoichiometric
energy efficient (lower operating conditions) pro- methodologies with atom-efficient catalytic alter-
cesses. The key steps of a catalytic process are: natives. Examples of process improvement via
catalysis include (i) the asymmetric hydrogena-
1. Diffusion of the reactant towards the catalytic tion of ketones and (ii) the production of hydro-
active site quinone, in particular:
2. Adsorption/Coordination of the reactant with
the catalytic active site

Chemistry,
Fig. 1 Schematic
difference between
homogeneous and
heterogeneous catalysis in a
batch reactor
Homogeneous Catalysis Heterogeneous Catalysis

Single Phase Multiple Phases
(i) Asymmetric hydrogenation of ketones: tra- the ketol and hydrogenation to the final product
ditionally carried out with DIBAL-H as [20]. Noncatalytic routes to propylene glycol
hydride donor, the process would culminate employed high temperatures and pressures
with stoichiometric amounts of aluminum (typically, >250 C and > 100 bar) [21], while
salts to be disposed [17]. The Noyori process the use of a catalytic material such as copper
was instead able to hydrogenate different chromite allows to drastically reduce the required
ketones with a Ru-based homogeneous cata- hydrogen pressure (<20 bar) at moderate temper-
lyst (Noble Prize in Chemistry, 2001) [18]. atures (<200 C) [22]. Additionally, the combi-
(ii) Hydroquinone production: originally pro- nation of catalysis with lower pressures was also
duced via aniline oxidation with manganese found to suppress by-product formation, thus
dioxide and Béchamp reduction with iron and improving atom economy [23]. In this sense,
hydrochloridric acid, inorganic salts gener- many researchers have put their effort in energy
ated in the process would add up to ten minimization through catalysis, with the final aim
times the amount of product generated. of running reactions at room temperature and
Solid ion exchange resins were found to cat- atmospheric pressure, with plenty of examples
alyze the aerobic oxidation to iso- found in literature [24].
propylbenzene with acetone as a From an engineering point of view, catalysis
by-product [19]. can also be a tool for inherently safer chemical
processes. In fact, mass and heat transfer limita-
The above examples clearly show how cataly- tions in a given reaction carried out in a batch
sis is able to minimize waste production and reactor can cause the formation of hot spots and
improve atom economy, thus following the prin- pressures build-ups which could in turn induce
ciples of green chemistry. runaway reactions. When using a (micro-) contin-
Catalysis is also able to improve the energy uous flow reactor, mass and heat diffusivity are
efficiency of a process. A relevant industrial largely improved, enabling a better control over
example is given by the Dow Chemical the reaction parameters and confining the problem
pharmaceutical-grade propylene glycol produc- in the apparatus [25] (Fig. 2). For this reason,
tion from bio-derived glycerin (by-product of bio- reactions involving explosive/toxic/hazardous
diesel synthesis) via subsequent dehydration to
Batch Reactor Continuous -Flow Reactor

Fixed residence times Variable contact times
Required catalyst/product separation Fixed catalytic bed eases product separation
High reactor volumes Scalable reactor volumes
Thermal and mass gradients difficult to Thermal and mass gradients easy to control
control (mixing-rate dependent) (flow-rate dependent)
Runaway reactions difficult to control Runaway reactions easy to control
Catalytic
Feed Product
Bed
Nanocatalysis for Green Chemistry, Fig. 2 Main differences between batch and continuous-flow reactor with
schematic drawing of the two types of reactors
intermediates see an incredible benefit in being on Pd-catalyzed olefin cleavage shows the possi-
run in continuous flow. bility of working safely within the oxygen explo-
Furthermore, in this type of reactors, tempera- sive regime in continuous flow [27]. Other
tures can be raised above the solvent’s boiling examples of forbidden chemistry made safe can
point resulting in a gas phase reaction, or liquid be found within the same research group [28].
phase if pressure applied according to the simpli- Although a catalyst is defined as a substance
fied Clausius-Clapeyron equation (Eq. 1), allo- that remains unaltered during the course of a reac-
wing different chemistries with a straightforward tion, deactivation phenomena often occur making
scale-up [26]. For instance, renewable future pos- the material itself a source of waste. Heteroge-
sibility for the production of chemicals and fuels neous catalysts generally have longer lifetimes
relies on liquid processing of biomass. Thus, con- as opposed to homogeneous catalysts; however,
tinuous flow conversion of biomass will require they can become waste themselves. In situ and ex
higher pressures in the system as opposed to tra- situ catalyst regeneration can extend the solid
ditional gas-phase processing. catalyst lifetime, reducing the amount of metal
waste going to landfills [29]. On the other hand,
p DH vap 1 1
ln ¼ homogeneous catalysis suffers from enormous
p0 R T T0 drawbacks in catalyst recovery and recycling,
Clausius Clapeyron logarithmic equation generating auxiliary liquid waste in the catalyst
(1) quenching step, and removal from product mix-
ture (if possible). In fact, implementation of
T (K) operating temperature homogeneous catalysis is severely hindered by
T0 (K) boiling point at pressure p0 inefficient separation processes. Supercritical car-
p (atm) vapor pressure at T bon dioxide would be an easy-to-separate solvent
p0 (atm) vapor pressure at T0 if not its low compatibility with common polar
DHvap (J mol1) vaporization enthalpy organometallic catalysts. Polarity and density of
R (J K1 mol1) universal gas constant supercritical CO2 can be improved by the addition
of an organic solvent which undergoes volume
In this way, catalysis in continuous flow allows expansions (i.e., expanded liquid phases)
the development of safe and scalable processes. [30]. Industrially, common practice to recover
A recent publication from Kappe’s research group homogeneous catalysts is by the aid of biphasic
systems, producing copious amount of liquid effect of the support hydroxyls groups [36]. Good
waste. Water-soluble metal complexes catalyze performances can be achieved in silica-supported
the reaction at the interface with the organic- single-site catalysts for polymerizations, alkanes
soluble reactant, decreasing the overall efficiency hydrogenolysis, and alkanes and olefins metathe-
of the process. Scavenging and organic solvent sis [37]. Nevertheless, heterogenization by immo-
nanofiltration of molecular weight enlarged cata- bilization has yet to be proven cost, stability, and
lysts are also contemplated at an industrial level; activity competitive with the heterogeneous catal-
however, highly efficient and stable resins and ysis market at an industrial level [38].
membranes (respectively) need to be developed The advancement of the so-called nanoscience
[31]. Green chemistry advances in the homoge- has allowed the development of catalytically
neous catalyst recovery involve supercritical CO2 active nanoparticles at the interface of heteroge-
and/or ionic liquids [32]. However, trace amounts neous and homogeneous catalysis [39]. The nano-
of catalysts often leach to the organic phase and/or size of various metals allows the catalytic system
remain in the end product, widely limiting its to have activity comparable to homogeneous cat-
applications due to high purity products demand alysts and stability/separability of heterogeneous
and regulations. catalysts. In fact, nanocatalysts possess extensive
Immobilization of homogeneous catalysts is accessible (solid) surface area which gives a more
one of the areas of research attempting to create intimate contact between reactant and active site.
a system with the activity and selectivity of homo- In particular, the new trends in catalytic processes
geneous catalysis and the stability and recyclabil- call for the development of hydrothermally stable
ity of heterogeneous catalysis. Anchoring of the catalytic materials, as for the conversion of bio-
homogeneous catalyst onto a solid support can mass. The next paragraph is thus dedicated to
occur via covalent bonding or by simple adsorp- promising advances in nanocatalysis, with partic-
tion, achieved through grafting or in situ sol-gel ular distinction between metal and sustainable
[33]. This particular approach enables the disper- catalytic nanomaterials.
sion of well-defined catalytic systems (e.g., organ-
ometallics), which, contrary to heterogeneous
catalysts (irregular surface, defective sites), Nanocatalysis
would possess the same activity and selectivity
in any point of the catalyst surface. The excellent Perhaps the most known catalytic process is the
thermal and chemical stability of silica has made Haber-Bosch ammonia production developed at
this support the main choice for heterogenization the beginning of the twentieth century, revolution-
of organometallics [34]; however, other support izing the world’s food production thanks to the
are being investigated. Costly triazolium carbene, development of an efficient route for fertilizers
also known as Rovis catalyst, was successfully manufacture [40]. Thanks to Bosch’s laboratory
supported onto silica and polysterene and tested experiments and Haber’s scale up, fertilizers were
in a model stereoselective reaction [35]. Only synthesized with abundant atmospheric nitrogen
poor results were obtained with silica as support, gas and steam-reforming hydrogen, making obso-
while high yields and fair enantioselectivity were lete the previous and inefficient processes based
obtained with the polymeric support. Compara- on nitrogen fixation to nitric acid (Birkeland-Eyde
bly, solid single-site catalysts have been designed process) or cyanamide (Frank-Caro process)
similar to organometallics grafting, allowing a [41]. The industrial process would have likely
dispersion of active metal sites with consistent been unfeasible without the development of a
activity and selectivity. Crystalline supports were nanocatalyst based on magnetite/wüstite (Fe3O4/
found to enhance the stability of grafted catalytic FeO) and promoted against sintering by K, Ca, Si,
sites, such as for isolated Fe3+. In particular, crys- and Al oxides (BASF S6-10) [42]. At that time,
talline delaminated zeolite was found to better the concept of nano was only under development
stabilize the grafted iron species due to a chelating [43]. The correlation between size and catalytic
activity was first questioned by Boudart later in The nanoscale state of these systems offers a
the 1960s, who supposed an intermediate ideal strong chemical bonding with an extensive delo-
size between atoms and bulk that would maximize calization of the electrons. Besides, the structural
the crystallite’s catalytic activity [44]. Later in the changes given by the confined space can induce
1980s, Haruta et al. discovered that catalytically different chemical and physical properties [47]. In
inert metal, gold, would possess exceptional oxi- fact, nanoparticles catalysts are often forced into
dation activity on an iron oxide support if smaller nonequilibrium shapes (e.g., platelet, rod, cubic)
than 5 nm. In fact, traditionally, (bulk) noble- which confer different catalytic properties, as
metal gold was considered as one of the least activity, selectivity, and accessible surface area
reactive transition elements with little-to-no appli- to the reactants. For instance, the internalization
cation in heterogeneous catalysis, although with of drug-releasing nanocarriers by the cell mem-
potential in oxygen transfer catalysis or as a dop- brane of a living organism is strictly dependent on
ant [45]. With the discovery of the remarkable the size and shape of the nanoparticles [48]. Thus,
oxidation activity at low temperatures of finely the synthesis of specific size and shape nano-
dispersed gold nanoparticles, Haruta et al. enlight- particles is crucial to obtain highly active and
ened the importance of the size effect on the selective catalytic systems with the advantage of
catalytic activity of materials [46]. A new gold easy separation and reusability.
rush had started, and the power of nanoparticles Advances in syntheses of materials through
was beginning to take shape. physical, chemical, or biological methods and
The particular advantages of catalysis in the surface characterization allow the design of highly
nano size lie in the higher efficiency, activity, functional nanoparticles with different surface
and selectivity typical of homogeneous catalysts, energies and morphologies [49]. In general, nano-
and the higher stability of the heterogeneous particles syntheses follow either a top-down or a
counterpart. A particle is considered nano if of bottom-up approach, where:
nanometers dimensions, being bigger of an atom
and smaller than bulk materials (Fig. 3). • Top-down approach: the nanoparticles are
The nanoparticles often have large surface-to- produced from a larger material by physical
volume ratio and sizes comparable to the reac- or chemical deconstruction. Ball milling of
tants, thus increasing the contact feed/catalyst, biomass is an example of a top-down approach
and overall accessible surface area. This particular to carbon nanoparticles.
feature enhances the catalytic activity and selec- • Bottom-up approach: nanoparticles are
tivity of the nanoparticles, mimicking the transi- arranged from smaller components (e.g., mol-
tion metal complexes employed in homogeneous ecules, quantum dots, other nanoparticles)
catalysis. On the other hand, their typical insolu- using chemical or physical means. Carbon
bility in common solvents allows the easy recov- nanotubes (CNT), for instance, are produced
ery and reuse of the materials. The green by a bottom-up approach (Fig. 4).
chemistry energy, material, and waste minimiza-
tion requirements are thus fulfilled in the nano
regime with the possibility of carrying out reac- Various well-defined morphologies nano-
tions at milder operating conditions, for longer catalysts based on different precursors (organic,
process times, and with a better atom economy inorganic) have been synthesized. In the next par-
thanks to the formation of less side stream prod- agraphs, the most notorious and recent examples
ucts. These materials possess exceptionally high in literature of different categories of nanocatalyst
surface areas and specific reactivity given by the for green chemistry will be given.
nano-dimension, as new properties appear when
the functional sites distribution narrows due to the
smaller dimension.
Atom Cluster Nanoparticle Bulk material
Å 1 nm 10 nm 100 nm μm
Nanocatalysis for Green Chemistry, Fig. 3 Schematic representation of a not-to-scale conventional classification of
atom, cluster, nanoparticle, and bulk material
Nanocatalysis for Green Chemistry, Fig. 4 Schematic representation of a top-down (above) and bottom-up (below)
approach to nanoparticles synthesis
Noble Metal Nanoparticles: Gold and intermediate between molecules and bulk metals.
Palladium In general, metallic nanoparticles are more active
with decreasing particle size, in particular:
Metallic nanoparticles are elemental nanoclusters
of a metal that can be amorphous, crystalline, or 1. Exposed surface atoms increase with decreas-
single crystallites (nanocrystal). The contiguous ing particle size
electron energy levels of the nanoparticles confer 2. Defective atoms (at the edges, in the corners)
to the system peculiar electronic properties also increase with decreasing particle size

Chemistry,
Fig. 5 Representation of
dispersed nanoparticles
(in gold) over a
(i) disordered porous
support (e.g., carbon black)
and (ii) ordered porous
support (e.g., zeolite)
Thus, small nanoparticles with a high number marking the era of the “Au rush” [54]. Due to
of defects will possess high catalytic activity the environmental and health harmful effects of
[50]. In general, shape and size will influence carbon monoxide, its oxidation increased the sci-
greatly the activity of a nanoparticle. In fact, entific interests in the past decades. The common
these two parameters influence the surface free Pt/Pd catalytic converter (also known as three-
energy of a nanoparticle, which in turn influence way catalyst) in the car exhaust system is acti-
the reactivity of the system. The higher the surface vated at temperatures as high as 200 C, reached
free energy is the higher the catalytic activity, but only after a few minutes of starting an engine.
the lower the stability [51]. As metallic nano- Thus, within a few minutes of driving a car, a
particles possess high surface energy, the disper- breakthrough of carbon monoxide will occur. Car-
sion on a metal oxide or carbon support is the most bon monoxide oxidation is also an important
common strategy to stabilize the metal against model reaction for probing the carbon oxidation
sintering (Fig. 5). properties of a catalytic material [55]. The use of
Furthermore, the nanosize of the particles (noble) metallic nanoparticles is often limited by
limits their isolation and recovery from the reac- sintering and fast deactivation of the catalyst.
tion mixture by conventional techniques such as Thus, metallic nanoparticles are commonly dis-
filtration, making deposition of metal nano- persed on metal oxides systems, such as silica,
particles on an inert/synergistic support the most titania, alumina, to name a few. For instance, the
used stabilization technique for their dispersion low temperature oxidation properties of Au nano-
and stabilization. The nature of the support will particles supported on different metal oxides
control both the reactivity and stability of the found by Haruta and coworkers could be applied
nanoparticles, due to different metal-support to minimize the formation of polluting carbon
interactions and anchoring properties. For monoxide [56]. In particular, density functional
instance, tunable reactivity of Au nanoparticles theory (DFT) calculations and kinetic modeling
on carbon in the selective oxidation of styrene is data attribute the strong interaction between Au
achieved by variation of solvent polarity nanoparticles and CO to the high density of potent
[52]. Noble metal nanoparticles have been exten- under-coordinated sites in a nanoparticle of a
sively studied due to their remarkable catalytic determined size which provides optimal binding
activities in a plethora of reactions [53]. to carbon monoxide and oxygen [57]. However,
Haruta’s discovery on the particular low tem- sintering of size-sensitive Au nanoparticles causes
perature CO oxidation activity of finely dispersed fast deactivation of the catalytic activity, thus with
gold nanoparticles has made this metal perhaps inefficient lifetimes [58]. To further prevent
the most explored of the past few decades, sintering, Somorjai and coworkers coated Pt
metallic nanoparticles with mesoporous silica production, increasing the waste of the system
nanomaterials. The silica conferred exceptionally [68]. For instance, NaBr and sulfuric acid improve
high thermal stability to the nanoparticles (up to the activity of mesoporous carbon Pd-supported
750 C in air), without compromising in Pt active catalysts. The addition of heteropolyacid to the
site accessibility of the reactants thanks to the carbon support was found to give the optimum
mesoporous system. [59]. High activity of these acidity to the catalytic system, circumventing the
systems has allowed their employment in various addition of H2SO4 [69]. As agglomeration of
catalytic reactions such as ethylene hydrogenation nanoparticles is the main source of deactivation
and CO oxidation [60]. Nanoparticles coating is of the catalysts, different preventing approaches
thus proven as an efficient sintering preventing are being brought forth. Pd-supported silica nano-
system; however, a compromise on activity particles were coated by a mesoporous silica shell,
might be necessary. finding higher catalytic activities as opposed to
Gold-catalyzed oxidation reactions were also microporous shells [70]. Hybrid ligand-modified
investigated by Hutchings’ research group, such Pd nanoparticles supported on carbon were
as carbon monoxide oxidation [61]. The oxidation recently found active in hydrogen peroxide direct
activities of gold nanoparticles were also tested synthesis. Furthermore, although long-term sta-
for primary alcohols and hydrocarbons for impor- bility has to be further explored, a higher leaching
tant applications in the agrochemical and pharma- resistance was observed [71]. The use of coatings
ceutical industries [62]. Gold nanoparticles were and ligands might be a necessary solution to
extensively studied also by Corma and coworkers, improve the stability of dispersed nanoparticles;
with a particular focus to green and sustainable however, the overall cost of synthesis is increased.
chemistry. For instance, a safer process was Direct synthesis of hydrogen peroxide was
advanced by the research group by using gold found possible also with gold nanoparticles, as
nanoparticles in the chemo-selective oxidation of pioneered by Hutchings research [72], and also
nitro compounds without the accumulation of observed by Haruta and coworkers [73]. In par-
explosive intermediates [63]. A one-pot process ticular, gold nanoparticles were found to have a
for the synthesis of aromatic azo compounds was higher hydrogen peroxide formation rate as
developed by the same research group where gold opposed to Pd nanoparticles [74]. The use of
nanoparticles supported on titania are found to gold nanoparticles allows running the process at
possess dual functionality: activity in the reduc- lower temperatures and with shorter reaction
tion of nitroaromatic compounds, and in the oxi- times, improving selectivity, thus the overall
dation of the so-formed aromatic amine [64]. greenness. In particular, Pd-Au alloys were
Another green chemistry relevant reaction is found exceptionally active even in the absence
the direct synthesis of hydrogen peroxide. In of acid and/or halides. Choudhary et al. screened
fact, hydrogen peroxide is a powerful oxidant various metal promoters finding Au and Pt as
with water as solely by-product [65]. optimum for bimetallic Pd-based catalysts
However, hydrogen peroxide production could [75]. Thus, alloying Pd and Au catalysts can
be environmentally sustainable if produced from enhance H2O2 production, becoming an efficient
hydrogen and water. The main issue is the non- strategy for industrial applications. A recent work
selective formation of water through side reac- found that addition of organic functional groups
tions due to incomplete oxidations of the such as –SO3H and –NH2 to the Au-Pd support
reactants or hydrogenation of the product [66] (e.g., SBA-15) was found to improve the system
(Fig. 6). Traditionally, metallic Pd is considered by enhancing hydrogen peroxide formation rate
the best catalysts for the direct synthesis of hydro- (acid groups) and suppressing the hydrogenation/
gen peroxide, thanks to its well-known remark- decomposition side-reactions thanks to the amine
able selectivity [67]. However, the presence of groups [76]. Mesoporous carbon was found more
acids and suitable anions (e.g., Cl, Br) is often convenient compared to microporous systems,
required to increase the hydrogen peroxide thanks to the enhanced diffusivity of hydrogen

Chemistry,
Fig. 6 Schematic
representation of the direct
synthesis of hydrogen
peroxide (green arrow), and
the undesired side reactions
to water (red dotted arrows)
peroxide with wider pores [77]. However, varia- by conventional methods (e.g., filtration). Separa-
tion of the oxidation state of the superficial species tion of the nanoparticles by applying a magnetic
and sintering after the first run of reactions still field appears to be highly promising.
limits the applications of these catalytic systems. The high oxidation tendency of metallic iron
Gold nanoparticles in general can find applica- (zero oxidation state), thus possessing
tions in a plethora of catalytic reactions, such as (dangerous) pyrophoric properties, has limited
additions to multiple C-C bonds, benzannulations, its applicability as bare catalyst [81]. Stabilization
and molecular oxygen oxidations of alcohols of iron nanoparticles by the use of a protective
[78]. A commercial application of a gold-nickel layer or the control of the reaction environment
catalyst is given by a Japanese methyl methacry- allows the use of metallic iron as catalyst, as
late production [79]. Nevertheless, current appli- hydrogenations under inert conditions. Nonethe-
cations are still limited by cost and stability. less, the oxidative reactivity of iron oxides nano-
Further improvements in the synthesis of gold particles has also been explored. In fact, the
nanoparticles with specific shape and sizes might different oxidation states of iron oxide nano-
improve their reactivity; however, sintering has to particles confer a potential of reactions, including
be stabilized [80]. aerobic conditions and hydrogen peroxide decom-
Growing concerns about the scarcity, toxicity, positions. In this sense, iron nanoparticles have
and cost of precious metal catalysts however is been employed in a large variety of reactions,
pushing the scientific community to the develop- including unsaturated hydrocarbon and alcohol
ment of cheaper, more abundant, and less harmful oxidations, oxidative coupling reactions, olefin
catalytic materials. In this sense, nonnoble metal, and carbonyls hydrogenations and transfer hydro-
transition metal oxides, and carbon-based nano- genations, as well as hydrogen evolution from
particles have been investigated. ammonia borane compounds [82].
The pioneering work by de Vries and
coworkers disclosed the reductive properties of
Nonnoble Metal: Iron/Iron Oxide Fe(0) nanoparticles [83]. Prepared by an inexpen-
Nanoparticles sive iron precursor, Fe(III) chloride, with three
equivalents of a Grignard metal reagent (e.g.,
As one of the 4th most abundant (hence, inexpen- EtMgCl), iron (0) nanoparticles (1–5 nm size)
sive) and environmentally friendly elements on were proven active in the hydrogenation of
Earth, iron is advancing as a valid catalyst substi- alkenes and alkynes under moderate conditions
tute to noble metals. The magnetic properties of (1 bar of H2, 25–100 C temperature range, up to
iron further increase the scientific interest as cata- 15 h). In particular, strained alkenes were found
lyst. In fact, as mentioned earlier, the small size of with a higher hydrogenation propensity as
the nanoparticles limits their separation and reuse opposed to linear alkenes, whereas alkynes
transformation could be tuned towards the alkene hydrogenation in 1:1 water/ethanol mixtures
or alkane depending on the catalytic residence [88]. The substitution of traditional hydrogenation
time. As often happens for the first works in an catalysts based on noble metals (e.g., Pt, Pd) can
innovative field, a few aspects of the catalytic be indeed achieved, upon protection of the
system had to be improved. The bare iron nano- metallic core.
particles were found highly susceptible to oxida- Iron oxides, on the other hand, have shown
tion and consequent deactivation. The absolute promising activities in oxidation reactions, as
absence of oxidants or moisture is required for well as stabilities. In particular, the iron oxidized
the stability of the system. Furthermore, the use states have been proven catalytically active in the
of Grignard reagents in excess copiously reduces industrially challenging selective oxidative cleav-
the sustainability of the synthesis. Finally, the age of hydrocarbons [89]. In particular, the ability
minute size of the nanoparticles hinders the mag- of iron of activating green reactants such as
netic properties of iron, thus their recoverability molecular oxygen and hydrogen peroxide has
and reuse. In an improvement attempt, Stein et al. made iron oxide particularly relevant in the selec-
synthesized magnetic Fe nanoparticles supported tive oxidation of alkenyl aromatics, olefins, and
on chemically derived graphene sheets by ultra- alcohols [90]. A wide variety of substrates were
sound degradation of Fe(CO)5 [84]. The work tested by Shi et al. [91] and Rajabi et al. [92],
used an environmentally friendly method in the proving the activity of iron oxide nanoparticles.
nanoparticles synthesis plus widely improved the By focusing their attention on styrene oxidation,
recoverability of the catalyst by magnetic decan- Rak et al. [93] emphasized the importance of a
tation. Bulk magnetization on small iron(0) nano- porous system. In fact, etched hollow Fe3O4 nano-
particles (ca. 2 nm) was also obtained by Chaudret shells were found more active as opposed to com-
et al. by the hydrogen-assisted reduction of an iron mercial Fe2O3 and Fe3O4 nanoparticles and core-
bis(trimethylsilyl)amide complex, found active in shell iron/iron oxide.
the alkene/alkynes hydrogenation under higher The different polyforms of iron oxide:
hydrogen pressure (10 bar), at longer reaction (i) magnetite, Fe3O4 (Fe(II,III) oxide),
times (20 h), and room temperature [85]. How- (ii) hematite, a-Fe2O3 (iron (III) oxide), and (iii)
ever, deactivation by oxidation is still a cause of maghemite, g-Fe2O3 (iron (III) oxide) confer dif-
concern. Coating of the Fe(0) nanoparticles ferent chemical and physical properties. Magne-
appears to be a promising strategy in increasing tite and maghemite bestow magnetic properties to
the stability of the system. Polyethylene glycol the final properties, while hematite is debated to
was used to protect the iron nanoparticles in the be the real catalytically active specie, in particular
ammonia-borane dehydrogenation [86]. The in H2O2-assisted selective oxidations. In fact,
polymeric shell allowed the reuse of the catalyst hydrogen peroxide decomposition rates were
for up to 10 cycles; however, strongly reductive largely enhanced by the presence of hematite, as
reaction conditions are required. Amphiphilic elucidated by the work of Hermanek and
polymers were also employed by Moores et al. coworkers [94]. Interestingly, higher hematite
to stabilize metallic iron in the alkenes/alkynes content improved the catalytic activity even if
hydrogenation in flow. Protection by the with lower surface area. Hematite was also
polystyrene-polyethylene glycol block copolymer found as the active specie in the oxidative cleav-
allowed the use of the catalyst in water-rich media age of lignin-model compound, isoeugenol,
up to 90% [87]. The same research group also towards high-end flavoring product, vanillin
investigated Fe(0) nanoparticles stabilization [95]. In particular, various carbon/iron oxide
with an iron oxide shell. The relatively big sized nanocomposites were prepared via environmen-
nanoparticles (ca. 50 nm) granted the magnetic tally friendly syntheses, namely, ball milling and
properties to the nanoparticles, making them solvent-free thermal decomposition, employing
recoverable, as well as stabilized the metallic inexpensive iron precursors and a relevant
iron core allowing to carry out olefins
chemical biorefineries by-product: humins 77 C) employing Co3O4 nanorods. The shape
[96]. The hematite- and hematite/maghemite- of the nanoparticle would preferentially expose
based catalytic materials (with or without mag- active Co3+ species on the surface, increasing its
netic properties, depending on precursor) showed activity and stability [100]. To a degree, the cata-
promising activities and selectivities in the lyst could find applications in aqueous environ-
microwave-assisted oxidation within 3 min of ments (such as the ones used in biomass
reaction. In particular, the hematite-carbon nano- conversion), thanks to stability of the catalyst in
composite was found the most active. On another the presence of water.
note, the particular use of a carbon material, Peculiarly, inexpensive metal oxides can find a
namely, humin by-products, appeared to further variety of applications in green chemistry. Arena
reduce the Fe oxidation state towards metallic iron and coworkers have studied low loaded iron
content as elucidated by SEM-EDX analyses. oxides/silica catalysts for the methane partial oxi-
This is a sign that carbonaceous materials have dation to formaldehyde prepared via an advanta-
the potential of reducing metal centers. This par- geous adsorption-precipitation route, although
ticular property could be applicable for the reduc- finding sintering and surface reconstructuring
tion of other metals. Nonetheless, further research phenomena [101]. Higher stability of the catalytic
on the catalytic activity of the various iron oxides nano-system can be achieved with a different
species is indispensable to further elucidate the preparation method. In fact, the same research
activity of Fe-based catalytic systems. group has also investigated the catalytic properties
of nanostructured manganese oxide with cerium
or iron as additives in a number of environmen-
Transition Metal Oxide Nanoparticles tally benign reactions, e.g., CO oxidation, pre-
pared via a novel redox-precipitation route from
Metal oxide nanoparticles have also attracted a inexpensive precursors [102]. In particular, the
fair deal of attention for their catalytic properties. redox-precipitation synthesis of the catalytic sys-
For instance, palladium oxide was found to be tems would enable a monolayer dispersion of the
more active and selective in the direct synthesis active phase, conferring a higher density of super-
of hydrogen peroxide as opposed to its metallic ficial active species with homogeneous morphol-
counterpart [75], attributed to a suppression of the ogies (spherical, ca. 10 nm) [103]. The
side reaction involving H2O2 decomposition manganese-ceria mixed oxide catalytic systems
[97]. Although catalytic activities comparable were found with optimum activities and stabilities
(or superior) to noble metal nanoparticles can be in CO oxidation, catalytic wet air oxidation, and
achieved with metal oxides, the main attractive- benzyl alcohol oxidation to benzaldehyde with
ness of oxide nanoparticles relies on their molecular oxygen [104].
mechanical or structural stabilities. In fact, nano- The biggest advancement of metal oxide nano-
structured metal oxides possess a lower surface particles for green chemistry applications lays in
energy, hence higher stability, compared to their electrocatalysis, in particular for oxygen reduction
bulk counterparts, as found for Al2O3, TiO2, and (storage of electrons, ORR) and evolution (release
VOx, to name a few [98]. For instance, microsized of electrons, OER) reactions for energy storage
alumina is most stable in its a form, while nano- and conversion (Fig. 7).
structured aluminum oxide appears to be more In fact, efficient energy storage systems (e.g.,
stable as g phase [99]. Also, a defined shape of batteries) could be used to store renewable ener-
the nanoparticles may play a highly influential gies (e.g., wind, solar) that are highly affected by
role in the catalytic activity of a material. The seasonal and daily changes. Generally, noble
importance of a defined morphology of metal metal bimetallic systems are used for ORR/OER
oxide nanoparticles was shed by Xie and cycling reactions, where Pt is active as an oxygen
coworkers, achieving moist-insensitive low tem- reduction catalysts, while Ir or Ru are active as
perature CO oxidation (temperatures as low as oxygen evolution catalysts [105]. Often the
Oxygen Reduction stability [109]. Yet, further understanding of the

mechanism of action of transition metal oxides, as
well as the effect of dopants and additives, is a due
–
→ –
in order to industrially implement cheap and
abundant oxides as metal catalysts.
–
→ – –
– –
→ –
Organic Nanoparticles: Carbon

Oxygen Evolution
Carbon is the 6th most abundant element in the
–
→ – universe and the most abundant in natural systems
after oxygen [110]. The number and variety of
Nanocatalysis for Green Chemistry, Fig. 7 Schematic allotropes make carbon materials highly versatile
representation of the oxygen reduction (above) and oxygen for different applications. In fact, the different
evolution (below) polymorphs possess different physical properties
to the carbon material, including density, surface
reactivity of one of the metals in the cycle can be area, and porosities [111]. In particular, nanostruc-
hindered by the presence of the other metal nano- tured carbon materials have attracted the attention
particles (antagonist reactivity) [106]. Limitations of the scientific community thanks to:
in the reactivity, as well as cost and limited
resources of noble metal nanoparticles, have • Abundance, thus inexpensive
pushed the scientific community towards transi- • Exceptionally high surface areas attainable
tion metal oxides. In this sense, manganese oxide (>1000 m2/g)
has attracted a fair deal of attention due to its • Tunable pore size distribution ranging from
remarkable redox properties, as well as abundance micro to macro
and price. A highly nanostructured manganese • Resistance to acids and bases
oxide inspired by nature was found exceptionally • Stability at high temperatures under inert atmo-
active for both oxygen reduction and water oxi- spheres (>1000 K)
dation, with activities comparable (or higher) than • Tunable functional groups and surface (from
the typical noble-metal catalysts [107]. The hydrophobic to hydrophilic, oxidized, etc.)
importance of morphology of the active phase is
also stressed in this field. In particular, a-MnO2 Thanks to these properties, carbon has been
was found the most active compared to b-, d-, and extensively studied as a catalyst support, owing
amorphous manganese oxides. The phase of man- to also the easy recovery of the active phase by
ganese oxide consisted of tunneled structures complete gasification of the carbon. Carbon mate-
(nanofibers) with small tetragonal structures, and rials allow a high dispersion of the metal nano-
the highest pore volume, as opposed to the other particles in the porous system, with the surface
manganese phases. These features, alongside a functionalities acting as anchors and stabilizing
higher presence of superficial Mn3+ species, the metal. Furthermore, the use of carbon as a
attributed high activity and stability to the cata- support grants an easy reduction of the metal
lytic system [108]. Nonetheless, manganese species at the most economical cost [112]. None-
oxides often suffer from poor conductivity which theless, the functional groups on the carbon sur-
limits their applications as electrocatalysts. To face have been found catalytically reactive, with
circumvent this problem, combination of metal activities comparable to metal catalysts [113]. In
oxides with more conductive materials (e.g., car- general, carbon materials catalyze the following
bon, stainless steel, titanium) is currently reactions: (i) oxidations/reductions (e.g., deNOx),
explored, with promising results in activity and (ii) hydrogenations/dehydrogenations (e.g.,
formic acid decomposition), (iii) decompositions In fact, carbon can form linear (sp), planar
(e.g., of hydrogen peroxide), (iv) dehydrations/ (sp2), and tetrahedral (sp3) bonds; however, inter-
polymerizations (e.g., poly-a-olefins production), mediate hybridizations exist (e.g., fullerene)
(v) isomerizations (e.g., a- to b-oximes), among [115]. Based on pore size, carbons can be classi-
others [112]. fied as microporous (<2 nm), mesoporous
Carbon catalysis would represent the ne plus (2–50 nm), and macroporous (>50 nm). Plus,
ultra in sustainable processes, if: porous carbon can be distinguished into disor-
dered and ordered (Fig. 9). Activity and selectiv-
• Resistance to gasification in high temperature ities of nanocarbons are often dictated by:
hydrogenation and oxidation reactions would (i) surface energy density in the case of micropo-
increase rous systems or (ii) surface functional groups for
• Reproducibility of the reaction activities mesoporous systems [116]. Macroporous carbons
would improve do not allow the necessary molecule confinement
• Heterogeneity of the carbon product is mini- for catalysis; microporous carbons often possess
mized, as impurities (mineral matter) are often diffusion limitations, being used mostly as adsor-
present depending on starting materials bents; mesoporous carbons, instead, are regarded
• Synthesis from renewable sources (e.g., bio- as the best compromise between heat/mass diffu-
mass) can be standardized in terms of quality sion and catalytic activity.
of product (random reconstruction, different Different conformations and crystalline orders
ash contents) of carbon nanomaterials can be achieved by
tuning the various synthesis parameters. For
In fact, the new trends in green chemistry cat- instance, synthetic method (catalytic) chemical
alytic reactions, such as biomass transformations, vapor deposition can yield different carbon nano-
see the employment of hydrothermal conditions structures by varying the operating conditions,
where a variety of metal oxides (e.g., TiO2, Al2O3, obtaining: (i) multiwalled carbon nanotubes,
mesoporous SiO2, zeolites) are unstable. For (ii) fishbone carbon nanofibers, or (iii) platelet
instance, zeolites may cover a pivotal role in bio- carbon nanofibers [117]. The formation through
mass conversion; however, the hot aqueous media synthesis of different functional groups, defects,
of biomass upgrade strategies severely impact the edges, sheets orientations, faces exposure will
stability of the aluminosilicates. Additionally, influence the catalytic activity and selectivity of
polar solvents deeply affect the nature of the the final carbon material.
active sites, their deactivation, thus long term Inorganic and organic carbon nanotubes
activities [114]. The typical hydrophobicity of (CNT) have attracted an enormous scientific inter-
carbon, instead, allows its use in certain condi- est thanks to their large surface areas, good elec-
tions, becoming extremely advantageous. These trical and thermal conductivity, and excellent
findings suggest that the typical petrochemical mechanical strength [118]. These nanomaterials
catalysts will be inefficient in the conversion of are composed of highly condensed curved gra-
biomass. Thus, the design of new catalytic mate- phitic layers with well-defined and nanosized
rials via the green chemistry principles can find an inner hollow cavities [119]. Praised for their inert-
answer in biomass-derived nanostructured ness, pristine carbon nanotubes have been exten-
catalysts. sively studied as support for metal (especially
Nanocarbons exist with different carbon atom noble) nanoparticles [120]. The functionalization
hybridizations (e.g., sp2 for graphene, sp3 for dia- of these materials via acid or bases treatments
mond, quasi sp2 for carbon nanotubes), giving allows the attainment of reactive surface groups
different electronic properties to the materials, (e.g., lactone, ketone, carboxylic, hydroxyl), thus
including conductivity and electron transfer higher catalytic activity [121]. Traditionally, these
(Fig. 8). materials are synthesized from high-energy
methods (chemical vapor deposition, arc
Diamond Graphite Graphene
Amorphous Carbon Carbon Nanotube
Nanocatalysis for Green Chemistry, Fig. 8 Structural representation of the different allotropes of carbon
Micropore
Mesopore
Macropore
Nanocatalysis for Green Chemistry, Fig. 9 Drawing of a disordered porous carbon (left) and ideal ordered meso-
porous carbon (right)
discharge, laser ablation, and spray pyrolysis) of of carbon nanotubes greener involve the use of
petroleum-derived precursors obtaining extensive vegetable oils as carbon feedstock (e.g., coconut,
sp2 hybridization (graphene-like) [122]. Often, turpentine, palm oil). For instance, CNT with
the preparation of these materials involves the diameters <2 nm were synthesized via spray
decomposition of the fossil compound by metal pyrolysis with an iron-cobalt catalyst from euca-
catalysts, making the process cost-ineffective. lyptus oil [123]. The study of different natural
Although efforts are currently ongoing in the effi- precursors (e.g., rocky sediments, clay, natural
ciency improvements of the synthesis process, the fibers) and/or catalysts based on volcanic residues
use of nonrenewable feedstocks and metal cata- (e.g., lava) has been also carried out; however,
lysts make their synthesis wasteful and impurities in the starting materials lead to inho-
unendurable. Attempts of making the synthesis mogeneous carbon materials [124]. Although
CNT from natural resources can be achieved, employing proteins, polysaccharides (e.g., dex-
other sustainable routes may be more advanta- tran), or glycine [128]. Nonetheless, the green
geous in the synthesis of (catalytically active) chemistry production of carbon nanomaterials
carbon nanomaterials. can be further improved by using renewable com-
Graphene oxide, a by-product from graphite pounds as opposed to graphite.
oxidation, has been researched as a cheaper alter- The active sites of graphene-based materials
native for graphene-like carbon materials include N- and P-dopants, defects, vacancies,
[125]. The reduction of graphene oxide yields to edges, sulfur groups, and especially oxygen func-
a material structurally similar to pristine graphene, tionalities. A DFT study on carbon materials illu-
reduced graphene oxide (rGO), that possess high minates the high activity of oxygen-containing
electron transfer abilities thanks to the sp2 hybrid- superficial groups on carbon materials, with qui-
ization. Full graphitization of the materials is none and lactone groups being the most active
often difficult to achieve, resulting in residual [129]. In this sense, biomass is an oxygen-rich
oxygen functionalities. Nonetheless, these oxy- carbon material, making it reasonable to produce
gen functional groups, alongside defective C-based catalytically active materials. Peculiarly,
edges, frustrated Lewis pairs, and carbon vacan- untreated soil, peat, and humic/fulvic substances
cies, have been recognized as catalytically active were found active in a number of condensation
sites. In fact, carbon-mediated catalytic activities reactions [130]. These premises, completed with
have been attributed to different oxygen- the knowledge gained on fossil-based carbon
containing functionalities, in particular: materials, allow the development of sustainable
carbon catalysts (or, support).
• (Hydro)quinone groups for hydrazine/hydro- Chemical and/or physical activation of bio-
gen peroxide/potassium peroxymonosulfate/ based precursors generally yields microporous
persulfate decompositions, selective reduc- carbons known as activated carbon. The simplic-
tions, (photo-)Fenton mineralizations, and ity of the activation method (e.g., NaOH
other advanced oxidation processes impregnation-chemical; steam gasification-
• Epoxy groups in SOx/NOx removal and aero- physical) allows the application to various carbon
bic oxidations based materials. Inexpensive resources, such as
• Benzyl alcohol-type groups in coupling reac- lignocellulosic biomass, coconuts residues, and
tions such as Suzuki-Miyaura C-H arylation of fruit stones, are typical substrates in the prepara-
benzene tion of activated carbons. These materials have
• Acidic O-H groups in alkylations, NaBH4- been extensively used as carbon supports for
mediated reduction of nitrophenols, or many heterogeneous catalysts, but most impor-
cyclocondensations to quinazolinone deriva- tantly find more interesting applications as super-
tives [126] capacitors for gas and energy storage for their
microporous range of pores [131].
Even so, rGO has been used as a support to Mesoporous carbons are a relatively new class
numerous metallic species, improving the cata- of materials which can be used as catalysts and
lytic activities for electrocatalytic oxygen reduc- prepared from natural resources. Tailoring and
tion reaction (ORR), photoelectrochemical design of the preparation method can yield homo-
hydrogen evolution, and catalytic oxidation to geneous porous systems in the range between
name a few [127]. However, the reducing agents 2 and 50 nm. In particular, hydrothermal carbon-
and surfactants used in the reduction of graphene ization and template-directed synthesis are taking
oxide are often toxic and harmful, as well as a hold of the scientific community in the synthesis
increasing the overall waste of the system. of truly sustainable carbon materials with regular
A sustainable reduction of graphene oxide with porosity and functional sites tenability. In this
bio-based molecules can be achieved by context, many isolated carbohydrates, whole lig-
nocelluloses, and urban/agricultural wastes have
been employed for the synthesis of nanocarbons. sorbents by chemisorption, for example, uranium
In particular, detailed 13C-NMR studies show and tetracycline removal [137], suggesting their
little-to-no difference in the final chemical struc- possible use as catalytic materials being adsorp-
ture of the material obtained via hydrothermal tion one of the crucial steps in a (heterogeneous)
carbonization of either isolated sugars or whole catalytic process (vide supra). In fact, hydrother-
biomass [132]. This suggests that mesoporous mal postmodification of carbon nanotubes in the
carbons can be produced from complex biomass presence of glucose, urea, and/or glucosamine
residues, without the need of hydrolyzing in order improved the oxygen reduction reaction activity
to obtain the isolated carbohydrate. for fuel cell applications by increasing the electron
The simplicity of hydrothermal carbonization density at the Fermi level [138]. Also, acid HTC
(HTC) makes it an advantageous synthetic proce- obtained by sulfonation or in the presence of
dure for carbon nanomaterials. HTC is a thermo- acrylic acid (vide supra) was found active in
chemical process for the conversion of C-rich biomass-relevant reactions such as cellulose
materials at elevated temperatures and pressures hydrolysis to glucose or fructose dehydration to
(often autogenous) in the presence of water. In HMF [139]. In general, HTC materials show
particular, high- and low-temperature HTC pro- lower-to-comparable activities to metal-
cesses can be identified, where the former is usu- containing catalysts. This slight drawback in
ally carried out in the 300–800 C range, while the activity could find justification in the low syn-
latter reaches only 250 C. Low-temperature HTC thetic cost of the potential material, even though
is applicable to bio-based materials within the further investigations are due in terms of long-
temperature stability range of the organic mole- term stability (for instance, in continuous flow)
cules. Dehydration, condensation, polymeriza- and preserved selectivities with longer reaction
tion, and aromatization are the reactions times.
governing the HTC process. In fact, HTC of bio- Although HTC is a simple and inexpensive
mass is believed to go via decomposition/dehy- procedure only involving a heated closed system
dration to soluble products (e.g., furanics, organic and water, thus advantageous and green, wide size
acids, phenols) and subsequent polymerization to distribution of the pores is often obtained. In order
the final carbon nanomaterial [133]. Activation to narrow the distribution, template-direct synthe-
temperature and time are important variables in ses are advancing in the production of carbon
the HTC of biomass. Nonetheless, the textural and nanomaterials. Generally two classes of template
morphological properties of the starting materials are distinguished:
will influence greatly the final properties of the
HTC carbon. In fact, compact textured biomass • Hard-template synthesis: the carbon nano-
materials will result in small surface areas, while particles are deposited onto a sacrificial porous
high porosity and surface area can be obtained inorganic template
from loose textured bio-materials [134]. Retention • Soft-template synthesis: sacrificial molecular
of the morphology of some types of biomass (e.g., or polymeric species stabilize the carbon nano-
pine sawdust) is achieved through microwave- particles into ordered mesophases
assisted hydrothermal carbonization, whereas
a-cellulose would yield spherical particles in the An example of hard-template synthesis is
same HTC conditions [135]. Hybrid carbon- given by the work of Titirici et al. who used a
polymer latex materials can be obtained by carry- variety of nanostructured silicas with different
ing out the HTC process of biomass in the pres- surface polarities as templates. By modifying the
ence of organic monomers. For instance, a functional groups on the silica and the carbon
carboxylate-rich (i.e., acid) carbon material was precursor loading, the research group was able to
obtained in a one-step HTC process of glucose obtain different morphologies of hierarchical car-
and acrylic acid [136]. Similarly to activated carbon: macroporous casts (very hydrophobic silica),
bons, HTC materials have been investigated as
hollow spheres (moderately hydrophobic silica), 4. Dissolution in acidic or basic media of the hard
mesoporous microspheres (60 wt% carbon pre- template, or carbonization of the soft template
cursor to silica), and simple carbon nanoparticles
(60 wt% carbon precursor to silica). In particular, Although defined structures can be induced on
a product of the acid conversion of a fraction of carbon nanomaterials, it is clear how this particu-
lignocellulosic biomass (in detail, hemicelluloses, lar synthesis does not follow the principles of
i.e., pentoses), furfural [96], was used as carbon green chemistry. In fact, the utilization of a sacri-
precursor [140]. By using a starch/gelatin ink in ficial template represents readily a waste, even if
the presence of silica spheres in 3D printing, a removed by heat and not inorganic acid or bases.
metal-free catalyst active in the selective oxida- A more sustainable approach along these lines
tion of benzyl alcohol was synthesized via hard was taken by the group of Clark et al., with the
templating [141]. In particular, the use of a 3D development of the Starbon ® materials. Starting
printer allows the easy and rapid synthesis of from starch, the research group was able to
different open structures with fewer limitations develop mesoporous carbons via controlled car-
in mass and heat diffusion. In fact, large open bonization. In particular the following steps were
porosities (>60%) gave systematically higher followed:
conversions over the studied reactions times with
slight improvements in selectivity. 1. Expansion of the starch macromolecules by
An example of a soft-template synthesis pro- thermal treatment in water
cedure is given by the surface coating technique 2. Cooling at 5 C to produce a retrograded starch
on a sugarcane bagasse scaffold. A phenol- gel
formaldehyde resin was employed as carbon pre- 3. Solvent exchange step with lower surface ten-
cursor with a triblock polymer (F127) as meso- sion solvents (ethanol, acetone)
structuring agent. A high surface area (ca. 500 m2/ 4. Carbonization/Pyrolysis of the mesoporous
g) was obtained upon removal of the polymer by starch
carbonization, with the micropore contributing at
66%. In this way, micro-meso hierarchically The obtained mesoporous carbons were found
porous materials have been obtained with superior to possess intermediate chemical properties
thermal stability [142]. In this sense, hierarchical between polysaccharides and activate carbons,
porous carbons for supercapacitor applications finding a variety of possible applications includ-
were synthesized in the presence of dioxane as ing catalysis and/or catalyst support [144]. None-
both solvent and mesopore-directing agent, acetic theless, recently Starbon® was found to be
acid as catalyst, and polymeric organic frame- exceptional sustainable sorbent for bioactive phe-
works (namely phloroglucinol, terephthaldehyde) nolic compounds [145]. The degree of carboniza-
as ultra/super-micropore-directing agent tion (proven tunable for temperatures between
[143]. The particular synthesis yielded to excel- 200 and 1000 C) influences the surface proper-
lent electrochemical properties, alongside a high ties of the highly mesoporous carbon, with tun-
specific surface area. able hydrophobicity/hydrophilicity and functional
Thus, in general both soft- and hard-template groups.
syntheses can be seen as multistep processes: The specific hydrophobic/hydrophilic environ-
ments of sulfonated Starbon ® materials were in
1. Synthesis of the template with predefined fact found advantageous over commercial micro-
porosity, or purchase porous carbons in the esterification of succinic
2. Deposition of the carbon precursor on the tem- acid, giving quantitative conversions and selectiv-
plate surface ities within 5 h of reaction time [146]. Not only the
3. Cross-linking of the precursor on the template higher hydrophobicity favored the synthesis of
surface mono-/di-esters in an aqueous environment, but
their mesoporosity positively influenced the mass Noble metal nanoparticles, the most studied so
diffusion of reagents and products. far, suffer mainly of deactivation by sintering;
As opposed to hydrothermal carbonization, the thus, there is a fair deal of research into their
synthetic procedure for Starbon ® materials calls stabilization. Commonly, dispersion on a support
for two extra pure solvents, and it might be is the popular method of preventing agglomera-
debated that the process is not sustainable. How- tion of the metal nanoparticles. Nonetheless,
ever, high purity acetone and ethanol can be pro- recent development on the field looks for the
duced by ABE (Acetone, Butanol, Ethanol) addition of ligands, stabilizers, and organic/inor-
microorganisms fermentations of biomass ganic coatings. However, this particular approach
[147]. Thus, with the collaboration of each field is against the 8th principle of Green Chemistry. In
of science, sustainability can be achieved. this sense, a different approach could be thought
Overall, carbon materials show potential as of: using of stabilized strong reducing supports
metal-free catalysts. In fact, depending on their (e.g., coffee/tea extracts on a hierarchically porous
superficial properties, different reactions can be carbon). In fact, if a reducing material is present
carried, such as oxidative dehydrogenations on the surface, oxidized/deactivated metal parti-
[148], esterifications/etherifications/alkylations/ cles would be in turn reduced. Nonetheless, noble
dehydrations/hydrolysis [149], as well as photo- metal nanoparticles are nonrenewable resources,
catalysis [150]. Nonetheless, their research is still and their use should be limited until complete
limited to traditionally inert inorganic carbons, substitution.
thus requiring the doping with a metal or metal Transition metals are generally more abundant
oxide. Further investigations of bare biomass- than their noble counterpart. Nonetheless, their
derived carbon materials might pave the future use as metallic nanoparticles is hindered as for
towards truly sustainable and renewable noble metals mentioned above. The employment
processes. of a more stable form, oxides, should be thus
favored. Elucidation on the metal oxides activity
mechanism is essential for their implementation,
in particular for the new emerging reactions, such
Future Directions
as biomass processing. Nonetheless, as noble
metals, transition metal oxides would also
The future can be green. The emergence of new
deplete.
technologies with renewability as a focus requires
Carbon nanoparticles are the future. As one of
further research in terms of chemical process. The
the most abundant elements, the most inexpen-
environmental impact of industrial chemical pro-
sive, the most equally distributed source of the
cesses can be copiously reduced by the employ-
planet, carbon shall cover a key role in the future
ment of catalysis, in particular nanocatalysis. In
sustainable and green processes. A carbon-based
fact, nanocatalysis bridges the activity and selec-
catalyst would be easily recovered, reused, and/or
tivity of homogeneous catalysts and the stability
disposed. Nonetheless, understanding of its
of heterogeneous catalysts. These properties
reactivity as well as improvement of its usually
imply energy and feedstocks savings in a chemi-
inhomogeneous porosity and stability is still
cal process, thus improving the environmental
required. Synthetic methods will cover a key
and economic impact of the production. Nonethe-
role in improving these properties, where methods
less, nanocatalysis is a continuously emerging
involving solvent-free thermal decompositions,
field, where new applications and reactivities are
mechanochemical activations (e.g., ball milling),
progressively discovered. The options are still
benign-solvent expansion, and pyrolysis should
boundless: the concept of nanocatalysis is merely
be preferred. Combination of different nature-
ca. 30 years old. Metal, metal oxide, organic are
derived compounds to create carbon nano-
the main categories of nanocatalysts, and all of
composites can largely improve the mechanical
these fields have large margins of improvements.
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Definition of the Subject

Nanocatalysis for Green

Nanocatalysis for Green

Homogeneous Catalysis Heterogeneous Catalysis

Batch Reactor Continuous -Flow Reactor

Atom Cluster Nanoparticle Bulk material

Nanocatalysis for Green

Nanocatalysis for Green

Oxygen Reduction stability [109]. Yet, further understanding of the

Organic Nanoparticles: Carbon

Diamond Graphite Graphene

Amorphous Carbon Carbon Nanotube

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