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Solanki and R. K. Sharma, New J. Chem., 2019, DOI: 10.1039/C9NJ01555H.

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New Journal of Chemistry Accepted Manuscript

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11 Metal Functionalized Carbon Nanotubes for Biomass Conversion:
12 Base-Free highly Efficient and Recyclable Catalysts for Aerobic
13
14 Received 00th January 20xx,
Oxidation of 5-Hydroxymethylfurfural
15 Accepted 00th January 20xx
Poonam Sharma,a Mohit Solanki,a and Rakesh K Sharmaa*
16 DOI: 10.1039/x0xx00000x
17 In this study oxidative conversion of 5-hydroxymethylfurfural into essential chemicals over recyclable metals (Pt, Pd, Ru, Co,
18 & Ni) supported catalysts are reported. While most of the catalytic reactions require base as an additive, current study
19 pertains to base free environmentally benign heterogeneous catalytic system. The reactions are carried out over various
20 M/CNT catalysts. As a support CNT plays an important role in the reaction mechanism. These catalysts show high activity for
21 base free oxidation of HMF under air in aqueous media. The CNT supported Pt, Pd, and Ru catalysts are found to be more
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22 selective towards FDCA (>97 %) whereas Ni and Co for DFF (>96 %). The conversion and selectivity of products are
23 determined by NMR and HPLC. The (1 wt%) M/CNT catalysts are prepared via solution processing and characterized by BET,
24 XRD, TEM, TGA, FTIR, and XPS.
25
26
27
28
29 Introduction Due to outstanding potentials of FDCA, catalytic conversion of
30 Biomass-derived commodity chemicals are getting significant
HMF to FDCA by oxidation in the presence of a base additive
31 attention as fossil resources are gradually diminishing. The
(Table S1) has been caught significant attention.11, 12 Selective
32 prices of fossil resource are increasing as most of the
catalytic oxidation of HMF gives various furan derivative
33 biorefineries depend on crude oil and natural gases. So, new
compound such as 2,5-diformylfurane (DFF),10 5-
34 technologies and processes are required that can help to
13
hydroxymethyl-2-furancarboxlic acid (HMFCA), 5-formyl-2-
35 overcome the urgent need for commercially interesting
furancarboxylic acid (FFCA), levulinic acid,14 γ-valerolactone,15
36 chemicals. Chemical transforms like biomass conversion can be
and 2,5-furandicarboxylic acid (Scheme 1).16, 17 In selected
37 one of the renewable energy sources that can provide a way to
reports, FDCA has been prepared by dehydration of mucic acid
38 overcome current problems related to fuels and other value-
in the presence of HBr and also by oxidation using KMnO4,
39 added chemicals.1-4
though these processes suffer from drawbacks, such as high
40 A variety of biomass-based chemicals like 2,5-furandicarboxylic
cost of oxidant and toxic wastes. Interestingly, electrochemical
41 acid (FDCA) and 2,5-diformylfurane (DFF) are the building blocks
oxidation of HMF using Pt electrode at basic pH gave DFF
42 of polyesters, bio-fuels, polyamide, and resins. Terephthalic
selectively while FDCA formed when TEMPO (2, 2, 6, 6-
43 acid (PTA) is an aromatic dicarboxylic acid, a petro product, used
tetramethylpiperidine 1-oxyls)-mediated oxidation under
44 for producing of polyethylene terephthalic acid (PET) polymer,
similar conditions though the separation of products has been
45 further used for the production of fibers, plant bottle, and
a challenge.18 Recently, aerobic oxidation of HMF has been in
46 various industrial applications. 5 An alternate of PET is
focus by using homogeneous catalysts and stoichiometric
47 polyethylene furandicarboxylate (PEF) that can be produced
oxidants such as Co(OAc)2, Mn(OAc)2, Co/Mn/Br and HBr and
48 from FDCA.6 Currently, FDCA based polymer is in high demand
NaBr with base and acid as an additive to produce FDCA and
49 due to low gas permeability and high glass transition
DFF.19 Despite good selectivity, these processes are not
50 temperature with high tensile strength.6, 7 FDCA is an oxidation
industrially viable due to non-efficient product separation and
51 product of 5-hydroxymethylfurfural (HMF) whereas HMF can be
poor catalysts recyclability. To over issues associated with
52 obtained by dehydration of carbohydrates (glucose, fructose).8,
homogeneous catalysts, development of highly selective
53 9 2-5 dimethyl furan (DMF) is an important constitute of biofuels heterogeneous catalysis has been resurgent of activity. A major
54 which can obtain by reduction of DFF.10
focus has been towards the development of non-reducible
55 oxide supported transition metal catalysts based on Ru, Au, Pt,
56 and Pd.20, 21 All these catalysts work only in the presence of alkali
57 [a] * Department of Chemistry, Indian Institute of Technology Jodhpur, Karwar, NH-
62, Jodhpur, India; [email protected]
metal hydroxides and carbonates with good to moderate
58 selectivity for FDCA. Ruthenium supported on MnCo2O3 can
59 Electronic Supplementary Information (ESI) available: work under acidic conditions with a good yield of FDCA in the
60

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3 aqueous reaction medium 22 while Ru/C performs well in the View Article Online

4 presence of Mg(OH)2 base as an additive and gives high DOI: 10.1039/C9NJ01555H

5 selectivity towards FDCA (97.3 %) with DFF as an intermediate.23

6 It is observed that Au has better catalytic activity than Pt, Pd, Ru
7 at pH 13.21, 24-26 Au/CeO2 catalyst was used to produce FDCA
8 under relevant condition (65 °C, 10 bar) in water in the presence
9 of NaOH (NaOH/HMF molar ratio 4) and also mentioned that

New Journal of Chemistry Accepted Manuscript

10 Au/CeO2 is more active towards oxidation of HMF compare to
11 Au/TiO2.12 Development of base free reaction for production of
12 FDCA has been very challenging because it produces additional
13 byproducts which make this reaction less selective and
14 environmental friendly at a high cost. Recently, Pd/Mg-Al-CO3 Scheme 1. Possible oxidation pathways of HMF to FDCA.
15 hydrotalcite catalyst has been reported with good catalytic
16 activity towards FDCA under base-free condition.27 Limited
17 studies pertain to carbon supported catalyst are mainly based Experimental
18 on TiO2/C,28 CoxOy-N@TiO2,29 Au-Pd/CNT, Pt/CNT30 that gave Material
19 moderate selectivity towards DFF and FDCA in the presence of
20 the variety of oxidizing agents at high temperature, however, 5-Hydroxymethyl-2-furfural (HMF, 99 %), chloroplatinic acid
21 metal leaching and irreversible deactivation of catalysts are (H2PtCl6, 37.50 % Pt basis), CNT (90 %), cobalt nitrate (Co (NO3)2.
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22 observed when the air was used as an oxidizing agent.17, 31-33 6H2O, 99.9 %) and palladium chloride (PdCl 2, 99 %) were taken
23 The metal leaching primarily happens due to poor bonding from Aldrich. Nickel nitrate hexahydrate (Ni (NO3)2. 6H2O, 98 %)
24 between support and metal particles. For that, carbon support and ruthenium chloride hydrate (RuCl3.xH2O, 99.9 %) from Alfa
25 especially carbon nanotube (CNT) has been proved to be an Aesar. Zero Air (20.4 % molecular oxygen) was supplied by the
26 excellent choice for support due to its extraordinary properties local source, and tap water was used as a solvent.
27 like uniform 1D sp2-bonded C-C bond, high surface area, good
28 electrical conductivity with anchoring functional groups.30, 34 Catalysts preparation
29 CNT can be tuned for controllable interactions with supported
30 metal nanoparticles with excellent chemical and thermal Generally, carbon materials are chemically inert, and we need
31 stability.35 The composite of metals with CNT can form stable to functionalize it before anchoring the metals on it. First, CNT
32 nanoreactors for catalysts conversion, qualifies CNT as an was sonicated with diluted HCl to remove the impurities and
33 adequate candidate for support material for heterogeneous further refluxed with HNO3 for functionalization for 2h at 140
34 catalysis. Our recent studies related to CNT supported catalysts ˚C. After this, CNT was washed with water followed by ethanol
35 30, 34 stimulate us to explore this work for base free HMF and dried under an inert atmosphere.
36 oxidation in water using molecular oxygen as an oxidant under The treated CNT was used in catalysts preparation. For that, our
37 ambient condition. previously reported method for the synthesis of metal loaded
38 Herein, we are reporting stable and recyclable multiwall carbon CNT catalysts were used.30 The catalytic preparation can be
39 nanotube supported noble (Ru, Pt and Pd) and non-noble (Ni explained by taking an example of Ru/CNT. An ethanolic
40 and Co) metal nanoparticles catalyst for base free aerobic solution of functionalized CNT was stirred and sonicated
41 oxidation of HMF in water. The functional groups present on simultaneously to prepare a homogenous solution of CNT. An
42 functionalized CNT play a crucial role in the synthesis of FDCA ethanolic solution of ruthenium salt (1 %, RuCl 3. xH2O) was
43 by increasing adsorption of reactant and intermediates.36 A added to the CNT solution via syringe pump under a hydrogen
44 comparative catalytic study of various metals loaded CNT for atmosphere and stirred for another 24 h at room temperature.
45 the aerobic oxidation of HMF in water is also reported. The Further, the solution was heated at 100 ˚C for 12 h and isolated
46 plausible reaction mechanism over supported CNT catalysts is via centrifugation, followed by washing with deionized water
47 proposed here. and ethanol. Ru tinted CNT catalyst was dried at 80 ˚C for 16 h
48 under inert atmosphere. Similar preparation process was used
49 for other catalysts, and these catalysts were pre-treated in the
50 tubular furnace in the hydrogen atmosphere for 3 h at 300 ˚C,
51 before the catalytic test.
52
53 Catalytic activity
54
55 The oxidation reaction of HMF is carried out in a 100 mL
56 autoclaves equipped with AMAR EQUIPMENTS PVT.LTD. Under
57 the optimized reaction condition, the autoclave charged with 10
58 mL water followed by the addition of a molar ratio of HMF to
59 catalysts (100:50). Further, the autoclave was purged two to
60

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3 three times with O2 and filled with cold pressure (30 bars) and shows signature peaks at 38.5°, 42.3°, 44.0° related to (100),
View Article Online

4 the temperature raised to 100 °C at stirring speed of 1200 rpm. (101), (110) crystal planes of the hexagonal lattice system
DOI: 10.1039/C9NJ01555H

5 Throughout this paper, the pressure is referred to as molecular (Figure 1f). All XRD patterns show that there is no change in
6 oxygen pressure. After 12h, the reactor was put for cooling by patterns of graphitized carbon after loading of metal.
7 terminating reaction process. Products were filtered by syringe-
8 filter and analyzed by HPLC and NMR. XPS analysis
9

New Journal of Chemistry Accepted Manuscript

10 Characterization XPS analysis was carried out to determine the state of metal and
11 the loading percentage of metal over CNT (Figure 2). The
12 An X-ray diffractometer, D8 advance (Bruker, U.S.A.) using Cu obtained binding energy of electrons helps to find out the
13 Kα1 (λ = 1.5 Å) as a radiation source was used to ascertain the oxidation state of metal. The C 1s peaks of functionalized CNT
14 quality and crystalline nature of metal loaded CNT with tube are observed at 284.2 eV, favored the presence of Sp2 carbon
15 current and voltage of 40 mA and 40 kV, respectively. atom while peaks at 532.8 and 531.6 eV are attributed to
16 Morphology and EDX mapping of M/C was determined using carbon-oxygen single and double bonds, including C-OH, C-O-C,
17 scanning electron microscopy (SEM, EVO18 Zeiss, accelerating C=O and O-C=O (Figures 2a). The values of binding energy for Ni
18 voltage 20 keV) and Bruker, respectively. The composite was 2p1/2 and Ni 2p3/2 are found at 878.8 and 859.5 eV,
19 pasted on silver tape for imaging. Transmission electron respectively.37 The characteristics peaks of Co 2p1/2 and Co 2p3/2
20 microscopy (TEM) was carried out in a FEI Tecnai-G2 T20. For at 801.17 and 783.16 eV correspondence to the metallic state
21 TEM study, the catalysts were dispersed in ethanol using tip of Co.29 The XPS spectrum of Pt metal shows that two peaks
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22 ultrasonication. The samples were prepared by placing a appeared at 71.12 and 74.54 eV belong to 4f 7/2 and 4f5/2,
23 droplet of suspension on to a copper grid and dried in air. denoting zero oxidation state of Pt.22 Pd gives peaks at 340.37
24 Oxidative products were characterized by NMR, HPLC, and eV corresponding to Pd 3d3/2 and 335.06 eV identified for Pd
25 polarimeter. Nuclear magnetic resonance spectra (1H NMR) 3d5/2 which indicate the metallic form of Pd.12, 38 Ru metallic
26 were recorded on a Bruker 500 spectrometer operating at 500 binding energy of 3d3/2 state was observed at 284.3 eV.39 These
27 MHz in D2O. Thermogravimetric analysis (TGA) was performed binding energy confirmed the zero oxidation state of metals
28 on TGA-6000 thermal analyzer (Perkin Elmer) under a nitrogen whereas some metals were found in +2 and +3 oxidation state
29 atmosphere (19.8 mL/min flowing nitrogen, the temperature which was further reduced for catalysis application. Metal
30 range of 30-900˚C, at the rate of 10 ˚C/min and pressure 3 bar) loading percentage was calculated using XPS and found ~0.9%
31 and a heating rate of 10 ˚C min-1. BET surface area was carried metal content which is near to the actual loading percentage.
32 out on the standard adsorption equipment (ASAP 2010,
33 Micromeritics Instruments Inc., Norcross, GA, USA) using N 2 gas TGA analysis
34 with 99.99% purity. High-performance liquid chromatography
35 (HPLC) from WATERS, Ireland was used to analyzing catalytic TGA analysis has been carried out to check the thermal stability
36 products. X-ray photoelectron spectroscopy (XPS) is performed of catalysts in the reaction medium (Figure 3). All M/CNT
37 using Omicron Nanotechnology spectrometer with catalysts are showing comparable weight loss till 200 °C due to
38 monochromatic. The curve fitting for XPS data is performed by desorption of moisture and volatile impurities, and further
39 Gaussian shape function with the help of using origin 9.0. slightly loss in weight percentage occurs due to metal contains.
40 TGA spectra show similar weight loss for all FCC containing
41 crystal structure whereas Ni and Pt loaded CNT catalysts show
42 a drastic drop in weight. It indicates less interaction of the metal
43 Results and discussion
with support. While Ru/CNT shows different Thermogravimetric
44 spectra, favors a different crystal structure of Ru. These
45 XRD analysis observations suggested that the thermal stability of these
46 catalysts depends on the chemical composition and
47 To determine the metal crystal structure and the effect of metal surrounding environment. All catalysts were presented without
48 loading on CNT structure, XRD analysis was carried out for all any decomposition and without any loss in their physical and
49 the catalysts (Figure 1). The X-ray diffraction patterns of chemical identities under our reaction temperature (373 K).
50 functionalized CNT shows characteristic 2θ value at 25.90°, Thus, it can assume that catalysts are stable up to 200 °C that is
51 42.70°, 53.50° associated to reflections (002), (100) and (004) a favorable condition for the oxidation reaction of HMF.
52 plane (Fig. 1a). Whereas characteristics peaks of Pt is recorded
53 at 39.68°, 46.4°, 67.7° analogous to dominating planes (111),
54 (200) and (220), respectively. XRD pattern of Pd obtained at
55 40.01°, 46.54°, 67.65° which is similar to Pt plane. The similar
56 planes were obtained in case of Ni and Co at 44.5°, 51.9°, 76.4°,
57
and 36.4°, 42.3°, 61.6°, respectively. The XRD patterns reveal
58
the face-centered-cubic structure of these metals whereas Ru
59
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Ni/CNT
5 300 C(002) Functionalised CNT
1800
C(002) Co/CNT 2500 Ni(111)
6 250
(a) (b) (c)
1700
7 2000 C(002)
Intensity (a.u.)

Intensity (a.u.)

Intensity (a.u.)
200
8 1600
1500
9 150 1500

New Journal of Chemistry Accepted Manuscript

Co(111) Ni(200)
10 100 C(001) 1400 Co (200) 1000
11 50
C(004)
1300
Co (220) Ni(220)
500
12 0 1200
13 20 30 40 50 60 70 80 20 30 40 50 60 70 80 20 40 60 80
2 2 2
14
15 7500
Pd(111) Pd/CNT
C(002)
Pt/CNT 1400
Ru(002)
Ru/CNT

16 (d) 3000 (e) 1200 Ru(101) (f)

17 Pt (111)
Intensity (a.u.)

5000 1000

Intensity (a.u.)
Intensity (a.u.)

C(002)
18 C(002)
2000 800
C(001)

Ru(103)
19 Pd(200) C(001)
2500 600
20 Pt(200)
Ru(100)
Ru(110)
Pd(220) Ru(102)
21 1000 400
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C(004) Pt(220)
22 C(004)
200
23 20 30 40 50 60 70 80 20 30 40 50 60 70 80 30 40 50 60 70 80
24  2 2

25 Figure 1. XRD patterns of (a) Functionalized CNT (b) Co/CNT (c) Ni/CNT (d) Pd/CNT (e) Pt/CNT, and (f) Ru/CNT
26
27
1300 220
28 C 1s
Pd 3d3/2 Pt 4f7/2
16000 Pt 4f 7/2
29
Intensity (counts/sec)

Pd 3d5/2
Intensity (Counts/sec)
Intensity (Counts/sec)

1100
1200 200 Pt 4f5/2
30
O 1s
Intensity (counts/sec)

1000 Sum Pt 4f 5/2

12000 Pd 3d3/2 Sum
31 900
1100 180
800
Pd 3d5/2
32 8000 700 1000 160
33 600
525 530 535 540
34 4000 Binding Energy (eV)
900 140
35
0 800 120
36 280 285 290 295 300 344 336 328 88 84 80 76 72 68 64 60
37 825
Binding Energy (eV)
900
Binding Energy (eV)
20000
Binding Energy (eV)
Ni 2P3/2
38 Co(0) 2P3/2 Ru 3d3/2
Ru 3p3/2
Intensity (Counts/sec)

Intensity (Counts/sec)

800 Co(0) 2P3/2 Ni 2P1/2

39 Sum
Intensity (Counts/sec)

Co(0) 2P1/2 850 Ni 2P3/2 16000

775 Sum
40 Co(0) 2P1/2
Sum
750 Ni 2P1/2 12000
41 800
725
42 8000
700 750
43
4000
44 675
700
45 650
0
46 810 800 790 780 770 760 890 880 870 860 850 840 290 288 286 284 282 280 278 276
Binding Energy (eV) Binding Energy (eV) Binding Energy (eV)
47
48 Figure 2. XPS spectra of (a) Functionalized CNT (b) Pd/CNT (c) Pt/CNT (d) Ni/CNT (e) Co/CNT, and (f) Ru/CNT
49
50
51
52
53
54
55
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BET surface area was obtained from N 2 adsorption-desorption
5 isotherms (Figure 5) and observed that after metal loading, the
80
6 surface area of CNT is decreased as showed in table 1. The
7 reduction of the surface area can be explained by clustering of
8 support particles during drying. It is also possible that some of
Weight (%)

60 Functionalised CNT
9 the reduction was caused by the blockage of micropores of CNT

New Journal of Chemistry Accepted Manuscript

Ni/CNT
10 by metal or support particles, reducing their absorption
11 40 Co/CNT availability of N2 molecules.
12 Ru/CNT
13 Pd/CNT Catalytic reaction
20
14 Pt/CNT
15 The catalytic activities were investigated for noble and non-
16 0 noble metal loaded CNT for HMF oxidation using Pt/CNT for
17 150 300 450 600 750 900 optimization. The process was optimized by varying pressure,
18 Temperature (oC) temperature and concentration. It was observed that maximum
19 conversion and selectivity was found at 30 bar O2 pressure with
Figure 3. TGA thermograms of noble and nonnoble metals
20 100/50 molar ratio of substrate and catalyst at 100 ˚C (Figure 6).
loaded CNT catalysts
21
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22 Under the optimization reaction condition, the entire series of

TEM analysis M/CNT catalysts were tested. First, we have tested noble metal
23
24 catalysts for HMF oxidation (Table 1). In the absence of metal,
The shape, size, and distribution of metal over CNT were functionalized CNT gave zero % conversion of FDCA and 87 %
25
characterized by HRTEM analysis (Figure 4). The CNT has an FFCA. While among noble metal loaded CNT catalysts, Pt/CNT
26
average length of 5 μm and the outer diameter of 6-9 nm. Figure catalysts gave good HMF conversion and excellent selectivity
27
4 (a, b) shows the morphology and open end image of towards FDCA, as observed before.40 High conversion of Pt/CNT
28
nanotubes at a higher resolution. It was observed from images is attributed to its excellent ability to abstract the β-H atom
29
that metal nanoparticle are well dispersed on the surface of from methyl hydroxyl side chain of HMF.41 The non-noble
30
CNT. Whereas at higher resolution image shows that metal catalysts nickel and cobalt are more selective towards DFF and
31
nanoparticles are encapsulated inside the surface of nanotubes. FFCA under optimized reaction conditions (Table 1 and Figure
32
The average particle size are calculated from TEM images and S11 & S12) which can be explained by conjugation of the
33
found between 2.4–15.2 nm (Table S2). Particle found inside the aldehyde group with the aromatic furan ring in the presence of
34
tube is smaller in size then outside. The TEM images of recycled Ni catalysts.42
35
catalysts reveal that there were no noteworthy changes in the
36
morphology and mean size of metal nanoparticles after Reaction mechanism
37
reactions (Figure S14). EDX mapping was confirmed the uniform
38
distribution of metal nanoparticles over CNT surface (Figure S1). Various reaction mechanisms of HMF oxidation have been
39
(a) (b) (g) (h) reported in literature,27, 36, 40, 43 indicated two probable routes
40
41 as sketched in Scheme 1. In route a, the aldehyde group is first
42 oxidized to form 5-hydroxymethyl-2-furancarboxylic acid
43 50 nm 10 nm 50 nm 10 nm (HMFCA), which is further oxidized to FFCA and finally to FDCA,
44 20 nm
(c) (d) (i) (j) whereas in route b, the hydroxyl (alcohol) group is first oxidized
45 to form DFF, a dialdehyde, followed by subsequent oxidation to
46 FFCA and then to FDCA. After characterization of products by
47 NMR and HPLC, it was found that route b could be the probable
50 nm 5 nm 50 nm 2 nm
48 path as no HMFCA was obtained as a side product or
(e) (f) (k) (l)
49 intermediate.23 Reaction through DFF is also supported to less
50 possibility of ring degradation as by-products. 36
51
50 nm 2 nm 50 nm 2 nm
52
53 Figure 4. TEM images (a, b) Functionalised CNT, and (c, d)
2 n m

54 Pd/CNT, and (e, f) Ru/CNT and (g, h) Pt/CNT, and (I, j) Co/CNT,
55 and (k, l) Ni/CNT
56
57
58 BET analysis
59
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12 Activated CNT = 299.8 m²/g 220 Pd/CNT= 228.5 m2/g Pt/CNT = 206.3 m²/g

Quantity absorbed (cm3/g STP)

Quantity absorbed (cm3/g STP)

Quantity absorbed (cm3/g STP)

250 140
200
13
14 200 (a) 180 (b) 120 (c)
160
15 140 100
150
16 120
80
17 100
100
18 80 60
19 50
60
40
20 40
0.0 0.2 0.4 0.6 0.8 1.0
21 0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0
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Relative pressure (P/Po) Relative pressure (P/Po) Relative pressure (P/Po)

22
23 Ni/CNT = 255.9 m²/g

Quantity absorbed (cm3/g STP)

180 200 Co/CNT = 280.7 m²/g
Quantity absorbed (cm3/g) STP

Quantity Absorbed (cm3/g STP)

Ru/CNT = 296.8 m²/g

24 160 180
2000

25 140
(d) 160 (e) (f)
1500
26 140
120
27 120 1000
28 100
100
29 80
80 500
30 60 60
31 40 40 0
32 0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0
Relative pressure (P/Po) Relative pressure (P/Po)
33 Relative pressure (P/Po)

34 Figure 5. BET-N2 adsorption–desorption isotherms of (a) Functionalized CNT (b) Pd/CNT (c) Pt/CNT (d) Ni/CNT (e) Co/CNT, and (f)
35 Ru/CNT
36
37
HMF
38 100 FDCA
100
39 DFF
90
Conversion & Yield (%)

Hyd.DFF
40
HMF Conv. and Yield %

FFCA
41 80
FFCA
HMF

42 70
FDCA

43 60
44 50 50
45
40
DFF

46
47 30
48 20
49 10
50 0 0
51 0 10 20 30 40 50
10

20

30

40

50

60
0

52
0:

0:

0:

0:

0:

0:

0:

Pressure (bar)
10

10

10

10

10

10

10

53
54 Substrate/Catalysts ratio
55 (a) (b)
56
57
Figure 6. Optimization of HMF conversion over Pt/CNT with (a) pressure, and (b) substrate/catalysts ratio (Reaction conditions: Pt
58
(1 wt %)/CNT, H2O (10 mL), 373 K, 12 h).
59
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11 Table 1. Catalytic behaviors of noble and non-noble metal nanoparticles loaded on CNT supports for the aerobic oxidation of
12 HMF.[a]
13
14 Selectivity (%)[e]
15 Metal
HMF
16 Entry Catalyst
loading[b] SBET(m2/g)[c]
Conv.
FDCA DFF FFCA Unknown
17 %
(%)[d]
18 Functionalized
19 1
CNT
0.0 300 86.5 0.0 0.0 86.82 0.0
20 2 Pt/CNT 0.96 206 100 97.8 0.0 1.3 0.9
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3 Pd/CNT 0.98 285 100 95.6 0.0 2.4 2.0

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4 Ru/CNT 0.90 297 100 92.8 0.0 6.1 1.1
23
24 5 Co/CNT 0.89 281 97.5 0.0 96.4 1.1 0.0
25 6 Ni/CNT 0.91 256 94.5 0.0 92.4 3.1 0.0
26 [a] Reaction conditions: HMF/catalyst (molar ratio 100:50), H 2O (10 mL), O2 (30 bar), 373 K, 12 h. [b] The metal loading was
27 ~ 1 wt%. [c] BET-N2 adsorption–desorption isotherms (Figure 5). [d, e] NMR and HPLC (Figure S2-S12).
28
29
30 A plausible mechanism of HMF oxidation is shown in scheme 2, oxidative dehydrogenation of the gem-diol in the presence of
31 in which hydroxyl group of HMF is adsorbed on the surface of supported catalysts (Figure S4 & S5). A similar process might be
32 M/CNT catalyst 27, 40 followed by C-H activation. Further two used for the formation of FDCA form FFCA (Scheme 2).
33 hydrogen atoms snatched from hydroxyl and C-H group and
34 removed by oxygen molecule like water. This mechanism CNT as a Catalyst
35 favoured the formation of DFF (Scheme 2, path 1). The To determine the catalytic effect of CNT, a test reaction was
36 nucleophilic groups like carboxyl, phenol and carbonyl/quinine carried out for the oxidation of HMF and observed that the
37 present on functionalized CNT surface attack on aldehyde group functional groups actively participate in the oxidation to form
38 of DFF and formed FFCA during hydrolysis (Scheme 2, path 2). FFCA (Table 1). Our investigation on the adsorption behaviour
39 In path 3, FDCA is produced by the same mechanism (path 2) of substrate and product on the CNT surface revealed that
40 from FFCA. Here metal nanoparticles play an important role by functional groups could enhance the adsorption of HMF as well
41 increasing the tendency of adsorption of the substrate and as the reaction intermediates from water and might facilitate
42 elimination of hydrogen by β hydride elimination.44 It is hydrogen transfer. It has been reported that the oxygen-
43 observed that O2 forms water by reacting with two hydrogen containing functional groups like carbonyl/quinone and phenol
44 atom, present on the surface of catalysts and cleans the surface groups, on CNT surfaces, play crucial roles in FDCA formation.40
45 of catalysts for further use.40 Adsorption of O2 over the metal The sp2 network of CNT play a key role in the adsorption of HMF
46 catalyst, lengthening of O-O bond distance observed, it is due to and furan contain products via π-π interaction.48-55 It has been
47 filling of antibonding orbital with electrons transferred from found that the FDCA has less tendency to adsorb on CNT
48 metal during the adsorption.45 Similar reaction mechanism has surfaces, favor both the conversion of HMF and the selectivity
49 been observed in the case of hydrotalcite support; in which of FDCA.36
50 hydroxyl group of hydrotalcite takes part in the formation of
51 FDCA and reaction proceed via a route a (Scheme 1).27 Catalyst stability and reusability
52
53 Yan and Dyson et al. suggested a new mechanism for the Recovery capability and stability are important properties index
54 oxidation of DFF by O2, in which they observed a gem-diol of practical heterogeneous catalysts. The stability of catalysts
55 intermediate for the formation of FFCA and FDCA. 46 Similar was tested by recyclability followed by ICP. The selectivity and
56 intermediates have been reported with HMF oxidase for yield% of FDCA and DFF were marginally decreased after 5
57 production of FDCA by route b.47. In this paper, we can also cycles (Figure 7 and Figure S13) which indicated that there was
58 suppose the formation of gem-diol intermediate by the no significant leaching of metal during the reaction. ICP analysis
59 hydration of DFF as the chemical shifts found with DFF and the indicated <1 ppm after 5 cycles.
60

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3 HMF FDCA 1. A. Corma, S. Iborra and A. Velty, Chem. Rev., 2007, 107,
View Article Online

4 100 2411-2502. DOI: 10.1039/C9NJ01555H

2. J. N. Chheda, G. W. Huber and J. A. Dumesic, Angew. Chem.
5

FDCA Selectivity
Int. Ed., 2007, 46, 7164-7183.
6 80 3. P. Gallezot, Chem. Soc. Rev., 2012, 41, 1538-1558.
HMF Conv.

7
8 60 4. R. A. Sheldon, Green Chem., 2014, 16, 950-963.
9 5. A. Gandini and M. N. Belgacem, ACS Publications, 2007, pp.

New Journal of Chemistry Accepted Manuscript

10 40 48–60.
11 6. C. Moreau, M. N. Belgacem and A. Gandini, Top Catal.,
12 20
2004, 27, 11-30.
13 7. A. J. J. E. Eerhart, A. P. C. Faaij and M. K. Patel, Energy
Environ. Sci., 2012, 5, 6407-6422.
14
0 8. A. A. Rosatella, S. P. Simeonov, R. F. M. Frade and C. A. M.
15 1 2 3 4 5 Afonso, Green Chem., 2011, 13, 754.
16 Recycling number 9. S. De, S. Dutta, A. K. Patra, A. Bhaumik and B. Saha, J.
17 Figure 7. Recyclability test of Pt/CNT. Mater. Chem., 2011, 21, 17505-17510.
18 10. H. Xu and C. Wang, Biofuels from Lignocellulosic Biomass:
19 Innovations beyond Bioethanol, 2016, 105-129.
20 Conclusions 11. R. Fang, R. Luque and Y. Li, Green Chem., 2016, 18, 3152–
21 3157.
Published on 31 May 2019. Downloaded on 6/1/2019 3:56:56 AM.

22 We have demonstrated that the noble and non-noble metal 12. N. Mei, B. Liu, J. Zheng, K. Lv, D. Tang and Z. Zhang, Catal.
23 nanoparticles supported on carbon nanotubes are efficient and Sci. Technol, 2015, 5, 3194-3202.
24 robust heterogeneous catalysts for the aerobic oxidation of 5- 13. Z. Zhang, B. Liu, K. Lv, J. Sun and K. Deng, Green Chem.,
2014, 16, 2762-2770
25 hydroxymethylfurfural in water under base-free conditions. In noble
14. J. J. Bozell and G. R. Petersen, Green Chem., 2010, 12.
26 metals, Pt/CNT, Pd/CNT, and Ru/CNT were tested for oxidation of
15. I. T. Horváth, H. Mehdi, V. Fábos, L. Boda and L. T. Mika,
27 HMF, and it was found that Pt/CNT has more selectivity and activity
Green Chem., 2008, 10, 238-242.
28 toward FDCA formation. Whereas non-noble metals, Ni and Co 16. I. Delidovich, P. J. Hausoul, L. Deng, R. Pfützenreuter, M.
29 loaded, CNT was selective towards DFF. The TEM-EDX analysis Rose and R. Palkovits, Chem. Rev., 2015, 116, 1540-1599.
30 confirmed the uniform distribution of metal nanoparticles on CNT. 17. O. Casanova, S. Iborra and A. Corma, ChemSusChem, 2009,
31 The XRD and XPS measurements confirmed that the metal particles 2, 1138-1144.
32 employed in this work were all crystalline and metallic, a favorable 18. Z. Zhang and K. Deng, ACS Catal., 2015, 5, 6529-6544.
33 condition for the oxidation reaction. A plausible mechanism is
19. X. Zuo, P. Venkitasubramanian, D. H. Busch and B.
34 Subramaniam, ACS Sustain Chem. Eng., 2016, 4, 3659-
proposed in this study based on analytical observation of 3668.
35 intermediate and products suggested that DFF undergoes 20. R. Sahu and P. L. Dhepe, REACT. KINET. MECH. CAT., 2014,
36
subsequent oxidation to 5-formyl-2-furancarboxylic acid (FFCA) and 112, 173-187.
37
then to FDCA through a tandem mechanism. The carbonyl/quinone 21. S. E. Davis, L. R. Houk, E. C. Tamargo, A. K. Datye and R. J.
38 Davis, Catal. Today, 2011, 160, 55-60.
or phenol groups on CNT enhance the adsorption of HMF and the
39 22. D. K. Mishra, H. J. Lee, J. Kim, H.-S. Lee, J. K. Cho, Y.-W. Suh,
intermediates DFF and FFCA and accelerate the formation of FDCA.
40 Y. Yi and Y. J. Kim, Green Chem., 2017, 19, 1619-1623.
41 23. L. Zheng, J. Zhao, Z. Du, B. Zong and H. Liu, Sci China Chem.,
42 2017, 60, 950-957.
43 Acknowledgments 24. K. R. Vuyyuru and P. Strasser, Catal. Today, 2012, 195, 144-
44 154.
45 25. A. Rass, H. Essayem, N. Besson and Michèle, Green Chem.,
The authors are grateful to acknowledge CASE facilities, IIT 2013, 15, 2240-2251.
46
Jodhpur, and DBT-PAN IIT centre for bioenergy 26. W. Gong, K. Zheng and P. Ji, RSC Adv., 2017, 7, 34776-
47 (BT/EB/PANIIT/2012) for financial support. We would also like 34782.
48 to acknowledge the Material Research Centre, MNIT Jaipur, 27. Y. Wang, K. Yu, D. Lei, W. Si, Y. Feng, L.-L. Lou and S. Liu,
49 India for providing a TEM characterization facility. ACS Sustain. Chem. Eng., 2016, 4, 4752-4761.
50 28. D. Gupta, K. K. Pant and B. Saha, J. Mol. Catal. Chem., 2017,
51 435, 182-188.
52 Conflicts of interest 29. L. Ning, S. Liao, Y. Sun, L. Yu and X. Tong, Waste Biomass
53 There are no conflicts to declare. Valor., 2018, 9, 95–101.
54 30. P. Sharma and R. K. Sharma, RSC Adv., 2015, 5, 102481-
55 102487.
56 31. Y. Y. Gorbanev, S. K. Klitgaard, J. M. Woodley, C. H.
References Christensen and A. Riisager, ChemSusChem, 2009, 2, 672-
57
675.
58
59
60

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Please do not adjust margins

 New do
Please Journal of Chemistry
not adjust margins Page 10 of 11

1 ARTICLE Journal Name

2
3 32. T. Pasini, M. Piccinini, M. Blosi, R. Bonelli, S. Albonetti, N. View Article Online

4 Dimitratos, J. A. Lopez-Sanchez, M. Sankar, Q. He and C. J. DOI: 10.1039/C9NJ01555H

Kiely, Green Chem., 2011, 13, 2091-2099.
5
33. M. Besson and P. Gallezot, Catal. Today, 2000, 57, 127-141.
6 34. P. Sharma and R. K. Sharma, New J. Chem., 2016, 40, 9038-
7 9041.
8 35. J. Nunes-Pereira, P. Sharma, L. Fernandes, J. Oliveira, J.
9 Moreira, R. Sharma and S. Lanceros-Mendez, Composi Part

New Journal of Chemistry Accepted Manuscript

10 B- Eng, 2018, 142, 1-8.
11 36. X. Wan, C. Zhou, J. Chen, W. Deng, Q. Zhang, Y. Yang and Y.
12 Wang, ACS Catal., 2014, 4, 2175-2185.
13 37. K. Gupta, R. K. Rai and S. K. Singh, Inorg. Chemi. Front. ,
14 2017, 4, 871-880.
38. Z. Ma, H. Yang, Y. Qin, Y. Hao and G. Li, J. Mol. Catal. Chem.,
15
2010, 331, 78-85.
16
39. D. Z. Austin, M. A. Jenkins, D. Allman, S. Hose, D. Price, C.
17 L. Dezelah and J. F. Conley Jr, Chem. Mater., 2017, 29,
18 1107-1115.
19 40. C. Zhou, W. Deng, X. Wan, Q. Zhang, Y. Yang and Y. Wang,
20 ChemCatChem., 2015, 7, 2853-2863.
21 41. J. Shen, H. Chen, K. Chen, Y. Qin, X. Lu, P. Ouyang and J. Fu,
Published on 31 May 2019. Downloaded on 6/1/2019 3:56:56 AM.

22 Ind. Eng. Chem. Res., 2018, 57, 2811-2818.

23 42. R.-J. van Putten, J. C. van der Waal, E. De Jong, C. B.
24 Rasrendra, H. J. Heeres and J. G. de Vries, Chem. Rev., 2013,
25 113, 1499-1597.
43. E. Hayashi, T. Komanoya, K. Kamata and M. Hara,
26
ChemSusChem, 2017, 10, 654-658.
27
44. A. J. Gellman, M. T. Buelow, S. C. Street and T. H. Morton,
28 J. Phys. Chem. A, 2000, 104, 2476-2485.
29 45. E. A. Ahmad, V. Tileli, D. Kramer, G. Mallia, K. A.
30 Stoerzinger, Y. Shao-Horn, A. R. Kucernak and N. M.
31 Harrison, J. Phys. Chem. C, 2015, 119, 16804-16810.
32 46. S. Siankevich, G. Savoglidis, Z. Fei, G. Laurenczy, D. T.
33 Alexander, N. Yan and P. J. Dyson, J. Catal., 2014, 315, 67-
34 74.
35 47. W. P. Dijkman, D. E. Groothuis and M. W. Fraaije, Angew.
36 Chem. Int. Ed., 2014, 53, 6515-6518.
48. D. S. Su, S. Perathoner and G. Centi, Chem. Rev., 2013, 113,
37
5782-5816.
38
49. E. Lam and J. H. Luong, ACS Catal., 2014, 4, 3393-3410.
39 50. X. Tan, W. Deng, M. Liu, Q. Zhang and Y. Wang,
40 ChemComm., 2009, 7179-7181.
41 51. W. Deng, M. Liu, X. Tan, Q. Zhang and Y. Wang, J. Catal.,
42 2010, 271, 22-32.
43 52. J. Zhang, X. Liu, R. Blume, A. Zhang, R. Schlögl and D. S. Su,
44 science, 2008, 322, 73-77.
45 53. A. Rinaldi, J. Zhang, B. Frank, D. S. Su, S. B. Abd Hamid and
46 R. Schlögl, ChemSusChem, 2010, 3, 254-260.
47 54. J. L. Figueiredo and M. F. R. Pereira, Catal. Today, 2010,
150, 2-7.
48
55. Z. Zhao, Y. Dai, G. Ge and G. Wang, ChemCatChem, 2015,
49 7, 1135-1144.
50
51
52
53
54
55
56
57
58
59
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Table of Contents
6
7 Aerobic oxidation of HMF over supported catalysts in water
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O
10 O O
OH O
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12 O
DFF
13 Biomass
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15 HMF Bio-fuel
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18 FDCA
19 O
M/CNT O
20 O
OH O O OH
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22 HO
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26 Noble and non-noble metal confined CNT based catalytic system developed for base free
27
selective oxidation of 5- Hydroxymethylfurfural to produce 2,5-furandicarboxylic acid and 2,5-
28
29 diformylfurane.
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