Mechanochemistry: Toward Sustainable Design of Advanced

Jun 14, 2018 - Mario J. Muñoz-Batista† , Daily Rodriguez-Padron† , Alain R. Puente-Santiago† , and Rafael Luque*†‡. † Department of Organ...
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Mechanochemistry: towards sustainable design of advanced nanomaterials for electrochemical energy storage and catalytic applications Mario J. Muñoz Batista, Daily Rodríguez-Padrón, Alain Rafael Puente Santiago, and Rafael Luque ACS Sustainable Chem. Eng., Just Accepted Manuscript • DOI: 10.1021/ acssuschemeng.8b01716 • Publication Date (Web): 14 Jun 2018 Downloaded from http://pubs.acs.org on June 15, 2018

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Mechanochemistry: towards sustainable design of advanced nanomaterials for electrochemical energy storage and catalytic applications Mario J. Muñoz-Batistaa, Daily Rodriguez-Padrona, Alain R. Puente-Santiagoa , Rafael Luque a,b* [a]

Department of Organic Chemistry, University of Cordoba, Campus de Rabanales, Edificio

Marie Curie (C-3), Ctra Nnal IV-A, Km 396, E14014, Cordoba, Spain. E-mail: [email protected] [b]

Peoples Friendship University of Russia (RUDN University), 6 Miklukho-Maklaya str., 117198,

Moscow, Russia KEYWORDS: mechanochemistry, nanomaterials, catalysis, electrochemical energy storage application, green chemistry ABSTRACT Mechanochemistry emerged as one of the most interesting synthetic protocols to produce new materials. Solvent-free methodologies lead to unique chemical process during the synthesis with the consequent formation of nanomaterials with new properties. The development of mechanochemistry as synthetic method is supported by excellent results in a wide range of applications. This feature article aims to highlight some representative contributions focused on protocols that could be easily extended to the synthesis of others advanced nanomaterials.

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Materials for batteries, supercapacitors and catalytic processes are discussed indicating the potential future directions of each field. Theoretical aspects and a revision of recent real in-situ analyses of the synthesis procedures are also featured. This contribution attempts to present, in a comprehensive way, the mechanochemistry as an open research line and a consolidated methodology to synthesize advanced nanomaterials. Introduction Inspired by biological processes on liquid water, the indispensable presence of solvents for chemical reactions have been a far old wrong assumption, which nowadays is still rarely questioned. Since solvents can disperse the heat, promote the interaction of reagents and facilitate, especially on a large scale, the efficient mixing, some reactions are not compatible with solventfree approaches.1–3 Nonetheless, solvent-free protocols possess energy and environmental advantages. Mechanical assisted synthesis can significantly reduce the reaction times compared to similar conditions in conventional solvent-based synthetic methods which in turn facilitate a substantial save on energy and cost.4–7An outstanding example is based in the synthesis of CuNHC complexes (NHC=N heterocyclic carbene).8 Lamaty and coworkers have synthesized five Cu-NHC organometallic compounds using a planetary ball mill. The materials obtained showed improved yields compared with the analogous reactions in solution due to the highly efficient mixing of the precursors in the process. Additionally, Bolm and coworkers have developed a solvent-free approach of iridium(III)‐catalyzed C−H bond amidation of benzamides with sulfonyl azides.9 The amidated products were obtained with higher yields and shorter reactions times (99 min) than those obtained by a conventional solvent-based chemistry (12h).10 In term of environmental benefits, these protocols constitute a desirable alternative to carry out in safety way reactions that require hazardous solvents by using solvent-free conditions. In these sense, the

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conventional methods for the synthesis of graphene usually involve toxic reagents which cause harmful effects on the environment.11 To avoid the use of hazardous reagents, Myung Jong Ju et al. developed an eco-friendly green synthetic process in which edge-selectively carboxylated graphene nanoplatelets (ECGnPs) were synthesized by the simple ball milling of graphite using dry ice (solid phase of carbon dioxide).12 Moreover, these processes have potential applicability due to their extreme simplicity, cleanliness, reproducibility and versatility.13 Therefore, alternative solvent-free routes, based on the grinding or milling of the reactants, have sparked the interest of the scientific community.14 Despite the long history of mechanical assisted reactions,15,16 the term “mechanochemistry” have been only recently formalized for the IUPAC into the chemical literature as: “a chemical reaction that is induced by the direct absorption of mechanical energy”.17 However, this terminology was introduced much earlier by Wilhelm Ostwald, who included mechanochemistry as part of physical chemistry and at the same level of thermochemistry, electrochemistry or photochemistry.18 Furthermore, Gerhard Heinicke in 1984 presented a widely accepted definition of mechanochemistry: “that branch of chemistry concerned with chemical ad physical changes of solids induced by the action of mechanical influence”.19 Despite the long history of mechanochemistry, most developments in this field have been reported from two decades ago. Mechanical forces can modify the energy scene of chemical reactions and create new reaction pathways, providing a synthetic approach which complements conventional chemistry. 20 During grinding, various processes take place such as mass transfer and the generation and relaxation of mechanical stress associated with the disruption of crystalline lattices.6 The mechanochemical processes involve several energies related to the cracking of crystals, the high defect density and

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the increase of the macroscopic temperature. Such energies can provoke the bond fracture and give rise to radicals in a different way to how occurs in solution.21

Theoretical aspects Along the history of mechanochemistry, various theories have been proposed. Among them, Bowden and coworkers settled down in 1952 the hot-spot theory, which established that due to the friction processes, high temperatures are generated on the surface, causing the initiation of the mechanochemical reaction.22,23 However, this idea was very criticized. Later on, the magmaplasma-model was proposed by Heinicke.24 In accordance with this model, at the contact spot of colliding particles, a tremendous amount of energy is produced, which is responsible for the formation of a special plasmatic state. The authors claimed that reactions can occur in the plasma or on the surface of particles and thus they do not obey to a unique mechanism. Furthermore, many other scientists have studied the mechanical-assisted reaction developing several theories and models.25–27 It is worth to point out, that unlike thermally assisted reactions, mechanical activated processes take place under non-equilibrium conditions, where the chemical reactivity is influenced by unbalanced

mechanical

forces.

In

addition,

mechanical

deformation,

and

therefore

mechanochemical transformation, take place locally, while temperature is an intensive thermodynamic state variable.28,29 Accordingly, it must be expected that mechanical and thermal conditions result in different mass transport processes and different physical and chemical behavior of the reactants.

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From a kinetic point of view, the mechanochemical reactions can be interpreted employing the collision theory, taking into account that the dispersing process and mechanical activation are statistically probable process.30 The kinetic energy, produced during the mechanochemical reaction can promote abrasion, fracture and the refinement of the system microstructure.31,32 In particular, fracture determines an increase of the surface area, improves the probability of contact between the reagents and therefore directly influences the rate of the mechanochemical reaction.33,34 In this regard, it was found that ethanol molecules interact with the active sites on the surface of fractured quartz particles, giving rise to hydrogen radicals. Besides, the crucial role of these sites was demonstrated by scavenger reaction experiments.35

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Figure 1. (A) Schematic representation of the setup employed to investigate mechanochemical synthesis by Raman spectroscopy and X-Ray Diffraction. Crystal arrangements of different metal– organic frameworks: (B) ZIF-8, (C) (H2Im)[Bi(1,4bdc)2], Crystal structures of (D) CoPhPO3•H2O and the (E) cocrystal theophylline:benzoic acid (1:1). Reprinted with permission from

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Copyright 2015 Wiley-VCH. (F) In-situ synchrotron X-ray diffraction analysis of MOF-74,

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obtained by mechanochemistry. Reprinted with permission from

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. Copyright 2016 American

Chemical Society. (G-I) In-situ X-ray diffraction results of katsenite and framework transformations. (Im correspond to imidazole, bdc to benzenedicarboxylate and Ph to phenyl, respectively). Reprinted with permission from 38. Copyright 2015 Nature. The mechanism of mechanochemical reactions has been challenging to study. In this regard, the grinding can be stopped after different intervals of time in order to study ex-situ the reaction mixture. However, this analysis is not accurate, especially when volatile compounds are involved in the reaction environment. In some cases, grinding is just required to provide the activation energy to initiate the reaction, which can go on without further milling. In-situ Raman spectroscopy have been recently employed to monitor a mechanochemical reaction, using a translucent chamber (See Figures 1A-E).36 The latest technique, together with in-situ X-ray diffraction, resulted to be a useful tool since they can offer different information content and possess different dynamic ranges.36 Noticeable, Friščić et al.38 performed a real-time study of a reaction progress by diffraction of high-energy synchrotron X-rays (Figures 1G-I). The preparation of a metal-organic framework,39 namely Zn-MOF-74 (Figure 1F), directly from a metal oxide by grinding was studied employing the aforementioned technique.37 In others very recently reports, in-situ reaction monitoring by synchrotron X-ray diffraction and numerical simulations of heat flow,40 and in-situ analysis using synchrotron X‐ray diffraction, Raman spectroscopy and thermography has been used to study milling reactions in real time.41 The combination of these methods allowed the simultaneously analysis of molecular, crystalline and temperature state of the material during the mechanochemical process. Nonetheless, in-situ investigations of reactions conducted by milling processes are still incipient and much more effort should be required for this purpose.

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Nowadays, most of the reaction mechanisms are inferred from ex-situ measurements such as Xray diffraction, solid-state NMR and FT-IR. In this regard, structural changes on Al-SBA-15, induced by milling with an iron precursor, have been investigated using diffuse reflectance infrared Fourier transform analysis. This technique, together with XRD measurements, revealed the formation of hydroxide species, supporting a reaction mechanism through the dehydroxylation of the materials.42 Equipment Mechanochemical reactions can be conducted using a wide range of conditions with several types of equipment.1 Mortar and pestle have been extensively studied, being one of the least expensive tools for mechanochemistry. Nonetheless, the employment of the aforementioned instruments is not reproducible, since it is not possible to strongly control reaction conditions such as frequency and strength.43 Cumbersome hand mortars have served as inspiration for the design of high performance grinder mortars with electronic control (Figure 2). Additionally, other specialized ball mills have been developed, including mixer mills and planetary mills. These instruments are recognized for the high energy milling and great control the reaction conditions. Mixer mills employ cylindrical flask oscillating horizontally, resulting in high impact forces between the ball bearing and the curved ends of the flask. In addition, planetary mills use a spinning vessel on an oppositely spinning sunwheel, providing high centrifugal and frictional forces on the materials. The latest ball mill generally allows a broader distribution of mechanical energy and the use of larger reaction volumes, while the mixer mill normally produces higher energy impacts.44 Another employed instruments include drum-mills and cryo-mills (for cryogenic grinding). In addition, novel designs of ball mill equipment have been recently developed in order to increase the energy input (high energy mills) by increasing the maximum speed to 2000 rpm and creating innovative

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grinding vessel designs. These instruments possess water cooling systems, which release the energy during the grinding process without sample overheating. Among the variables that affect the mechanochemical performance, the grinding speed, grinding time, reaction atmosphere, ball to-powder ratio and type of milling instrument are some of the most relevant ones. A variety of materials have been employed for the design of balls and vessels for mechanochemical reactions, including Teflon, alumina, zirconia, stainless steel and tungsten carbide.45

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Figure 2. Overview of the equipment for mechanochemical synthesis. (A). Planetary mills (vessels and equipment). Reprinted with permission from Fritsch (B) Mixer mill (vessels and equipment). (C) Grinder mortar. (D) Drum-mill. (E) Cryo-mill. (F) High energy mill (Emax). Reprinted with permission from Retsch. Advanced nanomaterials prepared by mechanochemistry

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Heterogeneous catalysts have gained increased attention since they play a crucial role in the development of the chemical industry.13,46–49 Indeed, the high activity and selectivity of solid catalytic systems have resulted in more efficient processes from both, economic and environmental points of view. Conventional methods for the preparation of catalytic materials include wet chemical precipitation, impregnation, sol-gel techniques, microemulsion, microwave assisted and hydrothermal synthesis, among others.50–53 Such procedures have shown several advantages and produced an extended number of applicable materials, but also possess inherent disadvantages related to the long reaction times, high temperatures and the use of solvents and additional reagents, which could have a negative effect on the environment. In this sense, mechanochemical synthesis has emerged as an outstanding approach with a high level of simplicity, reproducibility and versatility.54 This protocol has been used for the preparation of a wide range of nanomaterials with catalytic applications, such as supported metal and metal oxide nanoparticles, perovskites, nanocomposites, metal-organic frameworks (MOFs) and bioconjugates (e.g. based on proteins and metal oxide nanoparticles), as is schematically represented in Figure 3.55–64

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Bioconjugates

Supported metal nanoparticles

Co2O3

TiO2

Fe2O3

Catalysis

Carbon nanotubes

Mechanochemical synthesis

Energy storage

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Graphene-based materials

CuO

Metal oxide nanoparticles

GuaPbI3

Perovskites

UiO66 MOF-801

MOF

Figure 3. Representation of advanced nanomaterials synthesized by mechanochemical protocols for catalysis and electrochemical energy storage applications. Other advanced materials have been also prepared taking advantage of the remarkable possibilities of mechanochemistry. Among them, it have been reported the synthesis of BiS3 particles, which can possess potential applicability for biomedical imaging.65 In addition, the synthesis of monodisperse and ultra-small gold nanoparticles have been also described employing this outstanding technique without external reducing agents or bulk solvents.66

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Additionally, the continuous growth of the world population and the fast development of industry and technology have accelerated the global energy demand. Consequently, the consumption of traditional fuels has provoked serious effects on the environment, including global warming, air pollution, ozone depletion and acid precipitation, among others. In order to solve these issues, renewable energy technologies have represented an environmentally friendly alternative to traditional routes. Therefore, electrochemical energy storage devices based on low-cost abundant materials, such as nanocomposites, carbon-based nanomaterials, MOFs, and recently bioconjugates have been extensity investigated. In order to prepare such materials, mechanochemistry has been used as a powerful tool.67,68 Particularly, the synthesis of bioconjugates based on proteins and nanoparticles have been traditionally performed in solution being influenced by the environmental conditions, such as pH and ionic strength. In order to simplify their preparation, decreasing reaction times and environmental issues, related to the use of solvents and additional reagents, mechanochemical protocols have been employed for the first time in 2017. These studies have demonstrated that for proteins with high α-helix content, mechanochemical synthesis can be employed with preservation of their native-like structure (Figure 4).69

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Figure 4. (A) Schematic representation of mechanochemical synthesis. (B) Deconvoluted FT-IR spectrum in the amide I region of a BSA modified material. Adapted with permission from 69. Copyright 2017 Royal Society of Chemistry.

Electrochemical energy storage applications: Batteries and Supercapacitors In recent years, mechanochemistry has become in a powerful and promising alternative toward the fabrication of carbon based nanomaterials and hybrid protein-nanoparticles assemblies for energy storage applications, opening new horizons in the field of nano-energy. Along this section, we will focus our attention on electrochemical energy storage devices, namely batteries and supercapacitors, which are based on electron and ion charge/discharge.70–72 Nanocarbons such as carbon nanotubes (CNTs), carbon nanofibers (CNFs), carbide-derived carbons (CDCs) and graphene are some of the most widely used materials for the fabrication of ultrafast supercapacitors and highly efficient batteries.70,73–77 In this regard, surface activation by different chemical treatments and surface functionalization with O, N and B have been reported

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to enhance the electrochemical performance by providing pseudocapacitance, desirable surfaces areas, open pore structures and an additional number of Li-ion storage sites.78,79 Generally, during functionalization or chemical activation a high amount of hazardous solvents including acetonitrile, hexane, HF and H2SO4 are consumed, contributing to the environmental pollution. Additionally, most of these processes, such as impregnation, carbonization and washing, resulted in poor yields of the desired products. Mechanochemistry has been successfully applied to prepare anode materials for lithium-ion batteries (LIBs), based on FeO(OH)-nanoflake/graphene and nano-Fe3O4/graphene composites from commercial Fe powders and graphite oxides (GOs).80 Noticeably, mechanochemical processes promote the high contact between the metal and the GOs, facilitating the activation of the GOs reaction sites and in turn the formation of nanosized iron oxide on the surfaces of graphene. During the reaction, GOs was reduced by metallic Fe and exfoliated simultaneously to obtain graphene while the metal particles adopted a nanostructured flakes configuration (Figure 5A). The HR-TEM pictures of the nanocomposite confirmed the complete exfoliation of the GOs material indicating the high efficiency of the ball milling technique on the reaction yield. Consequently, XRD pattern of the nanoflake structures showed the disappearance of the typical peaks of the Fe and GOs phases with the concomitant emerging of new peaks (Figure 5B) which are ascribed to FeO(OH) phase.81 XPS spectrum (Figure 5C and 5D) supported the existence of a nanosized iron-based oxide phase onto the graphene structure. To obtain a Fe3O4/graphene nanoflakes, the as-synthesized FeO(OH)/graphene was calcined at 600 ⁰C in Ar atmosphere for 2 h.

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Figure 5. (A) Overview of the mechanochemical synthesis of nanocomposites based on iron oxides and graphene, (B) XRD analysis of the obtained nanocomposite, GOs and bulk Fe. XPS spectrum of FeO(OH)/graphene nanocomposite in (C) Fe 2p and (D) C 1s regions. Adapted with permission from 80. Copyright 2015 American Chemical Society. Notably, the nanoiron/oxide composite exhibited an outstanding performance as anode material for lithium ion batteries, with large specific capacitance values (around 980 mA·h·g-1) and outstanding cyclability. Such performance features are among the bigger values, at high current densities, reported in the literature for metal oxide based batteries,82,83 making this composite a promising candidate for the next generation of sustainable high-performance energy storage devices. The remarkable electrochemical behavior was ascribed to both, the nanostructured Fe3O4 framework and the excellent electron transfer properties of graphene, which create a suitable configuration for the volume changes during the charge-discharge process.

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Following a similar approach, Shao and coworkers have developed an easy methodology based on a mechanochemical strategy for the preparation of SnO2 nanocrystal/graphene composites.84 After grinding for 1, 2 and 8 h, GOs was reduced to graphene while Sn particles were oxidized to SnO2 nanocrystals and successfully adhered to the graphene sheets surface. The mechanically synthesized materials were used as anodes for LIBs. The electrochemical performance of the SnO2/graphene composite suggested that the ultrafine SnO2 nanocrystals together with the unique electronic properties of graphene improve the transport of electrons and lithium ions in the cell and in turn the specific capacitance and the cycling stability of the LIBs. Indeed, the battery delivered a first discharge capacity of 1737 mA·h·g-1 with a subsequent charge capacity of 1039 mA·h·g-1 at 0.1 Ag-1, and a reversible capacity of 891 mAhg-1. Mechanochemical methods have also allowed the synthesis of a nanocomposite based on Sn3P4 and phosphorus embedded in a graphene matrix (Figure 6A), as was revealed from XRD (Figure 6B) and further analyses.85 This material showed unrivaled high rate capacitance retention (>550 and 371 mA h g−1 at 1 and 2 A g−1), and outstanding rate capability as anode for sodium ion batteries.21 In addition, the authors have compared the electrochemical properties of ion sodium batteries based on SnP3, SnP3–graphene (SPG) and Sn4P3-P-graphene (SPPG). As shown in Figure 6C, the specific capacitance upgrade (SnP3 < SPG< SPPG) can be linked with the smaller particle size induced by higher energy mechanical milling, which improves the Na ion transport, as well as the stronger interactions between the active material and the graphene network.

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Figure 6. (A) Schematic illustration of the mechanochemical synthesis of SPPG (HEBM: high energy ball milling). (B) XRD patterns of SnP3, SPG and SPPG. (C) Capacity retentions and Coulombic efficiencies of the obtained materials. Adapted with permission from

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2015 Wiley-VCH. Ball milling synthesis has been used as an efficient method to produce materials with potential applicability as high performance supercapacitors from sustainable precursors. Particularly, nitrogen doped nanoporous carbons have been successfully prepared by mechanochemical approaches and applied on the design of this kind of energy storage devices. In this regard, C. Schneidermann et al. have synthesized N-doped nanocarbons with large specific area (up to 3000 m2/g) from lignin using a one-pot high-energy ball milling approach.86 The materials were employed as efficient supercapacitors, displaying an outstanding specific capacitance of up to 192

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F g-1 and a specific energy of up to 64.2 Wh kg-1 in an ionic liquid (1-ethyl-3-methylimidazolium tetrafluoroborate, EMIM-BF4) (Figure 7).

Figure 7. (A) Overview of the synthetic protocol for N-doped porous carbons- (B) Galvanostatic charge–discharge rate (at different currents) for activated carbon (YP-80F), lignin-urea-K2CO3_1 and lignin-urea-K2CO3_4. (C) Ragone plot in different solvent systems for lignin-urea-K2CO3_1 and lignin-urea-K2CO3_4. Adapted with permission from 86. Copyright 2017 Wiley-VCH. Another successful example consists in the mechanochemical synthesis of edge-nitrogenated graphene nanoplatelets (ENGNPs), in which nitrogen atoms were directly fixed at the edges of graphene nanoplatelets (Figure 8A).87 The cleavage of graphite flake by pin-grinding can create a

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number of active sites at the broken edges of the graphitic framework, which greatly favored the nitrogen doping processes. Mechanochemical processes triggered the fast sized reduction of starting graphite favoring the formation of small nanoparticles whose sizes can be tuned by the grinding time. Importantly, the surface area and pore volume of the nitrogenated graphene nanoplatelets increase proportionally with the grinding time. In brief, the nanoplatelets formed at high grinding times showed desirable properties for the fabrication of high performance supercapacitors. In fact, the specific capacitance of the ENGNPs formed at 7h was 202.8 F·g-1, which is two orders of magnitude higher than pristine graphite and approximately 31 units than the capacitance of the nanoplatelets formed at 5h (Figure 8B). The improvement of the electrochemical performance was ascribed to both the larger surface area and the higher amount of nitrogen at the edges of the nanocarbon network in the ENGNPs formed at higher grinding time.

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Figure 8. (A) Schematic illustration of edge-nitrogenated graphene nanoplatelets obtained by mechanochemical synthesis. (B) Specific capacitance of ENGNPs obtained at different grinding times. Adapted with permission from 87. Copyright 2016 Elsevier.

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Furthermore, a new strategy for the design of a bio-inspired supercapacitor has been proposed by our group.88 This work represents the first mechanochemical approach for the preparation of protein (hemoglobin) modified cobalt oxide magnetic nanoparticles. Firstly, a layer of dopamine was added by a ball milling step on the cobalt oxide surfaces with the subsequent anchorage of the protein over the dopamine modified nanoparticles. The nanobiomaterial was successfully used as a supercapacitor with a specific capacitance of 115 Fg-1 and an excellent long cycle life along with 94% specific capacitance retention after 1000 cycles (Figure 9).

Figure 9. Overview of the mechanochemical preparation and specific capacitance study of hemoglobin modified cobalt oxide magnetic nanoparticles. Reprinted with permission from

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Copyright 2017 Royal Society of Chemistry.

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Catalytic Applications In addition to the aforementioned advantages (green, cheap, easy synthetic protocols, etc.), mechanochemical approach emerges as a method to produce highly active and stable nanocatalyst. A wide range of catalysts have been synthesized by chemical transformations induced by mechanical compression, shear, or friction.13 With this in mind, the objective of this section is to give just an overview of representative mechanochemistry approaches for the synthesis of several new catalytic nanomaterials. As far as the fabrication of metal nanoparticles is concerned, mechanochemical allows addressing different strategies of synthesis. Several examples have shown that these protocols overperform the activity obtained by typical synthetic methods as chemical deposition or impregnation. A simple ball-milling procedure allowed the preparation active Ag/Al2O3 catalysts for the lowtemperature selective catalytic reduction of NOx with octane. This contribution reported for the first time the NOx hydrocarbon selective catalytic reduction at temperature below 200 °C (contrary to the catalyst prepared by typical impregnation method) without hydrogen.89 Furthermore, Au-Pd alloy and Au and Pd counterparts supported on P25 commercial titania and SiO2 have shown notable activity during oxidation of benzyl alcohol and direct synthesis of hydrogen peroxide. This study demonstrated that mechanochemical synthesized catalysts are more active than equivalent catalysts prepared by the impregnation route, indicating a better interaction between the component of the samples. This behavior leads to a beneficial synergistic interaction between the two metals.90 Others supports as walled carbon nanotubes can be used to produce highly active samples. In this remark, it is worth to highlight the mechanochemical preparation at room temperature (Figure 10C) of Pd on single (SWCNT)- and multi-walled carbon nanotubes (MWCNTs). The samples displayed a relatively good particle distribution (Figure 10A and 10B)

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and remarkable catalytic activity (Catalytic turn over number and turn over frequency of 7250 and 217 500 h-1, respectively) towards Suzuki cross-coupling reactions.91 In noble metal NPs, as well as the other advanced structures that will be subsequently discussed, the presence of additives obviously define the final properties and efficiency of synthetic route. In this regard, the role of saccharide additives during the mechano-synthesis of gold nanoparticles and their use as a catalyst in the reduction of substituted nitrobenzene derivatives into their corresponding aniline products have been recently reported. This is a very interesting case in which, the additive allowed at the same time, stabilization of the nanoparticles (Figure 10D and 10E) and selective formation of aniline products as is shown in Figure 10F. Authors showed that the catalytic performance strongly depends on the nature of the saccharide additive, the nature and location of the substituent and the grinding conditions.92

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C A

B

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Figure 10. (A) TEM micrographs and particle size distribution of Pd/MWCNT nanomaterial, (B) Overview of both, mechanochemical synthesis and further catalytic reaction. Adapted with permission from

91

. Copyright 2013 Royal Society of Chemistry. (C) TEM image and size

distributions of stabilized AuNPs. (F) Illustration of dynamics of exchange process between halogenonitrobenzene derivatives and saccharide additives. Adapted with permission from

92

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Copyright 2016 Royal Society of Chemistry. Transition metal NPs are also especially relevant for a wide range of catalytic applications. Using metallic rhenium and cobalt, Re-Co supported on Al2O3 catalyst has been prepared by

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mechanochemistry using high-energy shaker mill and argon atmosphere.93 In this contribution, samples obtained by mechanochemistry showed higher activity for methane conversion compared to the Re-Co/Al2O3 synthesized by impregnation. On the contrary, for CO hydrogenation, the catalysts prepared using traditional incipient wetness impregnation displayed better activity. The authors explained the opposite behavior based on clear morphology differences which lead to different kind of active sites. H2 obtained by steam reforming of methanol has been also used as model reaction to compare samples prepared by mechanochemistry and others typical procedures. In the work of Lu-Cun Wang et al., Cu/ZnO catalyst obtained by a facile solid-phase mechanochemical activation of a physical mixture (copper/zinc salts and oxalic acid), showed better catalytic performance compared with samples prepared using conventional co-precipitation methods. Favorable morphological properties were induced by the solid-state oxalate-precursor synthesis.94 Metal oxides obtained by mechanochemistry constitute also a new route for obtaining catalytic materials. In this regard, particle shape/size modification, structural disordering and defects in the crystal structure sometimes lead to interesting and new catalytic properties.13 A recent article developed a family of mesoporous transition-metal doped ceria catalysts with high surface area by mechanochemical (higher than state-of-art reported) grinding for CO oxidation.95 In photocatalysis field, several TiO2-based materials obtained by mechanochemistry have been reported.96–100 ZnO is another semiconductor suitable for efficient photocatalytic applications. Analysis of ZnO nanoparticles synthesized by mechanochemistry using various polysaccharides as sacrificial templates has previously reported for phenol photodegradation.101 Presence of two oxides has shown also superior photocatalytic properties. For example, mechanochemically prepared SnO2ZnO photocatalysts exhibited enhanced photochemical activity as compared with single phase

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SnO2 and ZnO. The heightened photocatalytic activity of the binary SnO2-ZnO was attributed to both higher surface area and improvement of the separation of photo generated charge from the coupling of ZnO with SnO2.102 Well-defined structures can be also prepared by mechanochemistry. Fabrication of 3D mesoporous black TiO2/MoS2/TiO2 nanosheets for visible-light-driven photocatalysis has been very recently published.103 The sandwich-like nanosheet structure was synthesized using a facile mechanochemical process in combination with an in situ solid-state chemical reduction treatment and calcination under an argon atmosphere. Recently, graphitic/graphene carbon nitride (g-C3N4) based materials have received special attention to achieve high photocatalytic activity.104 ZnO- and Fe2O3-g-C3N4 composite materials obtained using ball milling processes, and their subsequent use in the selective oxidation of benzyl alcohol to benzaldehyde has been reported.105 SEM and XPS results indicated that the enhancement of the activity and selectivity to benzaldehyde were associated with the concentration of the metal component as well as the homogeneity on the surface. A solvent-free approach, including two steps; ball milling and thermal degradation, has been also studied to produce humin-based iron oxide catalytic nanocomposites. The prepared samples showed high activity and stability during microwave-assisted oxidation of isoeugenol to vanillin.106 Besides to aforementioned applications of bioconjugates, our group has extended the mechanochemistry synthesis experience to produce active bioconjugate-based catalysts. In particular, a biocatalyst was synthesized by mechanochemical milling processes using horse hemoglobin and dopamine hydrochloride and a pre-synthesized Fe2O3 magnetic nanoparticles.107 The work showed for the first time, as is schematically presented in Figure 11A, a one-step synthesis of highly luminescent carbon-based polymers at room temperature. In addition, the highly efficient direct oxygen electro-reduction by partially unfolded laccases immobilized on

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waste derived magnetically separable nanoparticles has been also recently published (Figure 11B). The high efficiency of the bioconjugate (Figure 11C) was associated with conformational and structural changes in the immobilized laccase.108 The active Fe2O3 support in both contributions was previously synthesized using an iron precursor and orange peel waste as a template also by mechanochemistry and a subsequent calcination process in air atmosphere.

A

B

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D

B Figure 11. (A) Overview of the oxidative polymerization of phenylenediamines catalyzed by a hemoglobin based bioconjugate (Bottom images: poly-o, m and p- PDA and UV-irradiated (365 nm) samples. Adapted with permission from 107. Copyright 2018 Royal Society of Chemistry. (B) Overview of the direct electrocatalytic reduction of oxygen by laccase based bioconjugates, (C) Cyclic voltammograms of nanobioconjugates (blue line) in comparison with laccase free (red line), (D) Chronoamperometric behavior of laccase based nanobioconjugates performed under oxygen purging at 0.35 V. Adapted with permission from 108. Copyright 2018 Royal Society of Chemistry. Perovskite-like materials are also stable structures suitable for the catalytic applications. A mechanochemical procedure to produce these catalysts has been published in a series of studies by

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Kaliaguine et. al.109–111 The approach consists in a simple mechanochemical treatment which only required a controlled simple stepwise grinding of different metal oxide precursors. Catalytic properties of LaFe0.8Cu0.2O3, LaMn1−xCuxO3, LaCo1−xCuxO3 were systematically evaluated for NO reduction under different operating conditions. Calcium-containing perovskites (CaTiO3, CaMnO3, CaZrO3, and Ca2Fe2O5) as catalysts have also been reported.112 The study highlights that pure perovskite phase exhibited lower or no catalytic activity at 60 °C for methanolysis of sunflower oil. However, CaTiO3 and Ca2Fe2O5 samples which contained small amount of CaO exhibited catalytic activity at 60 °C. The work presented data which partially explain some contradictory statements reported in literature related to biodiesel synthesis at mild temperatures catalyzed by perovskites. Development of porous materials has been also studied using mechanochemistry as syntetic method. In this regard, our group has shown an intense activity developing materials for several catalytic-related applications. Using a mechanochemical approach, Al-SBA-15 has been modified with Fe2O3.42 The samples showed excellent catalytic properties for microwave assisted oxidation of benzyl alcohol and alkylation of toluene.113 Similar materials also showed activity during hydroarylation of phenylacetylene to 1,1-diarylalkenes,114 and hydrogenation and hydrogenolysis of lignin.115–117 Valorization of glucose by catalytic reactions have been also investigated. A formic acid-promoted dehydration and further selective hydrogenation to 5-methylfurfuryl alcohol have been shown as a way to glucose valorization.118 The reactions were carried out using Cu nanoparticles supported by two types of aluminosilicate materials; with and without Zn. Results indicated that Zn plays a desicive role in the selectivity of reduced products. Special interest has shown magnetically separable materials. The development of magnetic-based catalyts according to a simple one-pot scheme (Figure 12) focused on the use of mechanochemistry

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has resulted in excellent performance for Suzuki cross-coupling reactions (different types of aryl bromide/chloride with phenylboronic acid). This protocol allowed the preparation of these materials by simply grinding of solid Fe(NO3)3.9H2O, an appropriate quantity of propionic acid, Pd acetate and the SBA-15 support.61,119

Figure 12. Overview of mechanochemical preparation protocol of magnetic functionalized SBA15. Reprinted with permission from 119. Copyright 2014 Wiley-VCH.

Mechanochemistry has also opened new routes to synthesized and modified zeolites. Here, we highlight a catalytic application of hierarchical zeolites modified with iron oxide nanoparticles. The contribution compared the samples obtained by microwave‐assisted impregnation and mechanochemical grinding. Different acidity and morphological properties defined the catalytic activities in the microwave assisted alkylation of toluene with benzyl chloride. The authors detected an interesting synergetic effect between Fe and Al in the modified zeolites.120 The potential of Metal–Organic Frameworks in many applications have also been discussed extensively. These ordered structures have also shown good results in different catalytic applications. In this sense, similar to aforementioned materials, mechanochemistry can be used for

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both synthesis of the material or their subsequent modification with other entities which sometimes induce new advantageous properties. Zn(II)-based metal-organic frameworks (TMU-4, TMU-5 and TMU-6, see Figure 13A-G) prepared by a simple mechanochemical approach have been used in Knoevenagel condensation reactions.121 The structures contained azine-functionalized pores which conferred new active sites and catalytic properties. The study also showed a relatively good stability after several reaction cycles of reaction. Another reusable MOF structure for the aerobic Chan-Lam coupling prepared via ball-milling strategy have been also reported. Figure 13H, shows the Cu2(BDC)2(BPY) structure obtained by mechanochemistry and its application in the crosscoupling of aromatic amines and phenyl boronic acid. The authors optimized the metal ion and organic linkers in order to synthesize the structure properly.122 As last example, Zinc-based ZIF-8 structure modified with nickel clusters has been susccefully prepared by a one step mechanochemical procedure.123 Figure 13I shows an schematic representation of the protocol and Figure 13J evidence of the photocatalytic activity under visible illumination.

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A

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Figure 13. Schematic representation of TMU-4, displaying (A) the interpenetrated network and pore channels, (B) the pores (azine groups: blue balls). (C) Illustration of TMU-5 showing the pores (azine groups: in blue). Illustration of TMU-6, (D) Binuclear Zn2 cluster (O: red; N: blue; C: grey; and Zn: pink), (E) porous structure, (azine groups: in blue), (F) threefold interpenetrated network and pore channels. (G) Catalytic reaction. Adapted with permission from

121

. Copyright

2014 Royal Society of Chemistry. (H) Overview of the synthesis of Cu2(BDC)2(BPY) by ballmilling and its catalytic application. Adapted with permission from

122

. Copyright 2017 Royal

Society of Chemistry. (I) Representation of zinc-based ZIF-8 structure obtained by mechanochemical synthesis. (J) Photocatalytic results. Adapted with permission from. Copyright 2014 Royal Society of Chemistry.123

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Conclusions and Outlook Through this review, a general outlook of the current advances in the mechanochemistry field has been provided. In particular, we have focused our attention on the design of advanced materials with catalytic and electrochemical energy storage applications. Although there is still a long way to go in order to fully understand the behavior and mechanism of the mechanochemical reactions, a marked progress has been recently achieved. In this regard, both in-situ and ex-situ experiments employing novel spectroscopy techniques have been developed. Friščić and coworkers have made noticeable contributions in this area, using outstanding techniques such as diffraction of highenergy synchrotron X-rays for in-situ measurements, which represent a superior level of characterization. Regarding to the applicability of mechanochemical synthesis of materials for electrochemical energy storage, nowadays it has been observed an increased interest in the scientific community. Most of the efforts in this remark have been concentrated on the preparation of carbon-based materials and just recently bioconjugates. Nonetheless, the acquired knowledge in this area can be extended to other materials with potential applicability in energy storage, including MOFs, transition metal oxide and nitride nanoparticles.124 Mechanochemistry have been more widely applied to the preparation of catalytic materials such as supported metal nanoparticles (Ag, Pd, Au, Cu, Co, etc.) and metal oxides (TiO2, ZnO, Fe2O3, SnO2). Recent advances in the field have been recovered in this review, passing through metal-organic frameworks, perovskites and proteinbased bioconjugates. Particularly, we envisaged that the recent use of mechanochemical routes for the synthesis of bioconjugates based on biomolecules, such as proteins and monosaccharides,125 may pave the way for further development of supramolecular assemblies with a wide variety of applications, not just

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for catalysis and energy storage devices, but for biotechnology and biomedical uses. In addition, mechanochemical synthesis has proven to be a useful tool in order to simplify the preparation of advance ordered structures like MOF. In this sense, mechanochemistry has contributed to the development of crystal engineering by tuning the crystal structures in order to obtain MOF with novel functionalities and improved surface areas and porosity.56 Although, theoretical studies have been performed to scale-up mechanochemical synthesis and nowadays some process in the industry involve grinding steps,126 further efforts should be devoted to correlate lab and industry results, considering milling rate and impact energy. Besides all the advances in mechanochemistry that have been achieved so far, the remarkable potential of this technique still lead to a wide range of possibilities. We hope that this perspective review can inspire the scientific community to take full advantage of the benefits offered by mechanochemistry, allowing the development of more sustainable and efficient synthetic processes.

ACKNOWLEDGMENTS Rafael Luque gratefully acknowledges support from MINECO under project CTQ2016-78289-P, co-financed with FEDER funds. Both Daily Rodriguez-Padrón and Alain R. Puente-Santiago also gratefully acknowledge MINECO for providing research contracts under the same project. Mario J. Munoz-Batista gratefully acknowledges MINECO for a JdC contract (Ref. FJCI-2016-29014). This publication has been prepared with support from RUDN University Program 5-100. Rafael Luque is also grateful to ACS for the ACS Sustainable Chemistry & Engineering Lectureship award, for which this Feature article was submitted.

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Mechanochemistry: towards the synthesis of advanced nanomaterials for catalysis and electrochemical energy storage applications.

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