ChemComm

Formation of gold nanorod-carbon dot nanocomposite with superior catalytic ability towards reduction of aromatic nitrogroup in water

Journal: Manuscript ID: Article Type: Date Submitted by the Author: Complete List of Authors:

ChemComm CC-COM-12-2013-049752 Communication 24-Dec-2013 Mandal, Pritiranjan; Ramakrishna Mission Vidyamandira, Department of Applied Chemistry and Industrial Chemistry Ghosal, Krishanu; Ramakrishna Mission Vidyamandira, Department of Applied Chemistry and Industrial Chemistry Bhattacharyya, Swarup; Ramakrishna Mission Vidyamandira, Department of Applied Chemistry and Industrial Chemistry Ganguly, Debabrata; Ramakrishna Mission Vidyamandira, Department of Applied Chemistry and Industrial Chemistry Das, Mithun; Ramakrishna Mission Vidyamandira, Department of Applied Chemistry and Industrial Chemistry Bera, Abhijit; Ramakrishna Mission Vidyamandira, Department of Applied Chemistry and Industrial Chemistry Gupta, R. K.; Pittsburg State University, Chemistry Marti, Angel; Rice University, Chemistry GUPTA, BIPIN; National Physical Laboratory (CSIR) , Materials Physics and Engineering Division; Rice University, IUSSTF Fellow (Indo-US Science & Technology Forum) Department of Mechanical Engineering and Materials Science, Rice University, MS-321 Maiti, Subhabrata; Ramakrishna Mission Vidyamandira, Department of Industrial Chemistry and Applied Chemistry

Page 1 of 18

ChemComm

Manuscript Title: Formation of gold nanorod-carbon dot nanocomposite with superior catalytic ability towards reduction of aromatic nitrogroup in water Authors: Pritiranjan Mondal,a Krishanu Ghosal, a Swarup Krishna Bhattacharyya, a Debabrata Ganguly, a Mithun Das, a Abhijit Bera, a R. K. Gupta, b Angel A. Mart, c Bipin Kumar Gupta* d and Subhabrata Maiti*a

Justification for publication

Nanotechnology has found tremendous attention towards catalyzing chemical reactions including their already established implication towards optics, electronics and so forth. The unique surface properties of noble metallic nanoparticles like gold, silver are being exploited in catalyzing diversified class of reactions ranging from carbon monoxide oxidation, C-C coupling to hydrogenation. The advantages of using gold nanostructures in modulating catalysis lie to their ease of synthesis in different forms, stability, surface functionalization etc. Typically, smaller nanoparticles showed higher catalytic ability in various kinds of reactions. However, in case of redox reactions, anisotropic nanostructures with high electron transporting ability like nanocage or nanobox have been observed to facilitate the catalytic rate. To this end, nanocomposite made of carbon nanostructures and metallic nanomaterials are evolving as excellent materials for nanocatalysis, photovoltaics to nanoelectronics. Among all carbon nanostructures, carbon dots (CD), the newest and exciting member of carbon family displays huge prospect towards sensing, biomedical as well as photocatalytic application because of its intrinsic photoluminescent properties. Surprisingly, exploitation of CDs in catalyzing redox type of reactions remains unexplored. To this end, CDs can also exhibit high electron transporting ability as it has an electron rich graphitic core. Therefore, a nanocomposite comprising CD and anisotropic gold nanorod (GNR) can emerge as a prospective material towards redox type of reactions. We have chosen the catalytic reduction of aromatic nitro groups (p-nitrophenol, onitrophenol, m-dinitrobenze) using NaBH4 as the model reaction to check the catalytic ability of the designed GNR-CD nanocomposite. The presence of CD increased the rate of electron transfer as well as firm localization of the reactant molecules within the catalyst and thus almost a 2-fold enhanced catalytic activity in compared to only GNR was found almost in every cases. The developed catalyst is stable in water as well as it has high recyclable efficiency towards catalysis. Most interestingly, the catalysis can also be efficiently performed with water-insoluble compound, like m-dinitrobenzene. Importantly, for the first time catalytic property of carbon dot in conjugation with GNR is utilized in reduction of nitroarenes and thus endorsing its effectiveness in designing various industrially important catalysts. The present investigation unveiling the effectiveness of carbon dot in conjugation with GNR towards catalysis of nitroarenes will find significant interest in the development of novel materials for nanocatalysis as well as its application in interdisciplinary branches of sciences will find significant interest in the development of novel materials and techniques for nanotechnology and thus it would find interest among the interdisciplinary readers of Chemical Communications.

Journal Name
Cite this: DOI: 10.1039/c0xx00000x www.rsc.org/xxxxxx

ChemComm

Dynamic Article Links Page 2 of 18

ARTICLE TYPE

Formation of gold nanorod-carbon dot nanocomposite with superior catalytic ability towards reduction of aromatic nitrogroup in water
Pritiranjan Mondal,a Krishanu Ghosal, a Swarup Krishna Bhattacharyya, a Debabrata Ganguly, a Mithun Das, a Abhijit Bera, a R. K. Gupta, b Angel A. Mart, c Bipin Kumar Gupta* d and Subhabrata Maiti* a
5

Received (in XXX, XXX) Xth XXXXXXXXX 20XX, Accepted Xth XXXXXXXXX 20XX DOI: 10.1039/b000000x We report the synthesis of gold nanorod-carbon dot nanocomposite and its utility as a recyclable catalyst for reduction of aromatic nitrogroup. Presence of carbon dot on gold nanorod surface enhanced the reduction rate by twofold. Nanotechnology has found tremendous attention towards catalyzing chemical reactions since the pioneering work of Haruta.1 The unique surface properties of noble metallic nanoparticles such as gold and silver are being exploited in catalyzing a variety of reactions ranging from carbon monoxide oxidation and carbon-carbon coupling to hydrogenation.1-3 The catalytic ability of metallic nanostructures is due to their size, shape and nature (e.g. hollowness and porosity).3-4 The advantages of using gold nanostructures in modulating catalysis lie in their straighforward synthesis in different forms, stability, and surface functionalization, among others.4-5 Typically, smaller nanoparticles showed higher catalytic ability in various kinds of reactions.5 However, in the case of redox reactions, anisotropic nanostructures with high electron transporting ability such as nanocages or nanoboxes have been observed toenhance the catalytic rate.4 Nanocomposites made of carbon nanostructures and metallic nanomaterials are emerging as excellent materials for nanocatalysis, photovoltaics to nanoelectronics.6-7 Among carbon nanostructures, carbon dots (CDs), the newest and exciting member of carbon family, are interesting prospects for sensing, biomedical and photocatalytic applications due to their intrinsic phophophysical properties.8
Department of Applied Chemistry and Industrial Chemistry, Ramakrishna Mission Vidyamandira, Belurmath, Howrah 711 202, India, E-mail: subhabrata.maiti@gmail.com. b Department of Chemistry, Pittsburg State University Pittsburg, KS 66762, USA c Dept. of Chemistry and Bioengineering, Rice University Houston, TX 77005 d National Physical Laboratory (CSIR) Dr K S Krishnan Road, New Delhi 110012, India ; E-mail:bipinbhu@yahoo.com Electronic Supplementary Information (ESI) available: Details of synthesis of GNPs and CDs, other experimental details, TEM images, UV-vis spectra, kinetics graph, see DOI: 10.1039/b000000x/
70 50

10

55

15

60

20

65

Surprisingly, exploitation of CDs in catalyzing redox reactions remains unexplored. For example, CDs is expected to exhibit high electron transporting ability due to its electron rich graphitic core. Therefore, we envision that a nanocomposite that synergitically combine CD and anisotropic gold nanorods (GNR) could have important applications in redox reactions. GNR stabilized with cationic cetyltrimethylammonium bromide (CTAB) can be conjugated with carbon dot having carboxylate functional groups. Notably, the designed composite might also offer several advantages: i) presence of anisotropic GNR which is already known for its high catalytic efficiency due to presence of different facets;9 ii) The availability of the graphitic core of CDs, which can expedite the transfer rate of electrons; and most importantly, iii) the hydrophobic domain between GNR and CD can help trapping hydrophobic molecules which would allow aqueous catalytic reactions of water-insoluble compounds. Thus, GNR-CD nanocomposite is an interesting approach for the development of superior nanocatalyst.

25

30

35

40

45

Fig. 1 a) UV-vis spectra, b-c) TEM images of synthesized GNR-CD nanocomposite ([Au] = 100 M, [CD] = 100 g mL-1) d) schematic representation of the formation of the GNR-CD nanocomposite.

This journal is The Royal Society of Chemistry [year]

[journal], [year], [vol], 0000 | 1

Page 3 of 18

ChemComm

10

15

20

25

Initially, we have synthesized GNR with a transverse surface plasmon peak (trans, SPR) at 520 nm and longitudinal peak (long) at 695 nm using standard protocols (Fig. 1a).10 Details of the synthetic procedure can be found in the electronic supplementary information (ESI). Transmission electron microscope (TEM) images revealed that the width of the GNR is 10 2 nm, having aspect ratio of 2.8 0.3 (Fig. 1b-c and S1a, ESI). The synthesized GNRs are highly stable as these are stabilized by the quaternary ammonium group of cetltrimethylammonium bromide (CTAB).10 In order to produce the GNR-CD nanocomposite, we have designed carbon dot functionalized with long chain anionic carboxylate (Fig. 1d). CDs were synthesized by thermal coupling between sodium-salt of 11-aminoundecanoic acid and citric acid as discussed elsewhere (Fig. 1d).11 Here citric acid acts as the carbon source and 11-amino undecanoic acid covalently linked with the carbon nanoparticle via amide bond. The size of the CDs are of 3 1 nm as found from TEM images (Fig. S1b, ESI). Also a negative zeta potential () value of -23.8 2 mV confirms the presence of carboxylate moiety on the surface of the CD. The synthesized GNR solution was centrifuged at 14,000 rpm for 90 min to remove excess CTAB and the residual material was redispersed in aqueous phosphate buffer (pH 7.0, 25 mM). This buffered GNR solution was then used to make the conjugate with CD functionalized with carboxylate moiety. The nanoconjugate was prepared by mixing GNR and CD solutions in phosphate buffer at different ratio. The formation of the GNR-CD

45

50

55

60

65

70

role in nanocomposite formation (Fig. 1d). To test the catalytic ability of the synthesized nanocomposite, we have chosen the reduction of p-nitrophenol as the model reaction.12 The conversion of p-aminophenol from its nitro analogue is a reaction of versatile applications that includes antipyretic or analgesic drug development, dye industry, and corrosion removal.13,14 Moreover, the reaction does not proceed in absence of any catalyst. The progress of the reaction can be easily monitored by observing the rate at which the characteristic 400 nm peak of p-nitrophenol decreases as it converts to paminophenol, with a generation of a new peak at 300 nm (Fig. S2 and S3a, ESI). The reaction followed pseudo first order kinetics as the concentration of NaBH4 is in excess (almost 1000 times higher) than that of p-nitrophenol. Initially, we have monitored the apparent rate constant (kapp) of the reaction in presence of varying concentration of GNR ([Au] = 10-100 M). We have observed an increase in kapp (from 0.05 to 0.072 s-1) with increasing Au concentration up to 50 M and then remain almost constant (Table S1, ESI). At this point, the GNR-CD composite was fabricated by varying CD concentration from 12.5 to 100 g mL-1 while concentration of GNR was kept constant (50 M). Increasing GNR concentration resulted in colloidal instability of the composite. Interestingly, an increase in the CD concentration in the GNR-CD composite (up to 50 g mL-1) led to a 2-fold increase in the kapp from 0.072 to 0.143 s-1,while further increase in the CD concentration (100 g mL-1) caused almost no effect in the kapp at 0.135 s-1 (Fig. 3 and S3, ESI). However, presence of only CD led to an almost negligible effect towards catalyzing the reaction (Fig. S3, ESI).

Fig. 2 Fluorescence spectra of CD in absence and presence of GNR of varying concentration (Inset: Visual fluorescent image of CD).

30

35

40

nanoconjugates was confirmed both by spectroscopic and microscopic method. The strong photoluminescence properties of the CD (emission and excitation wavelength maxima = 420 and 340 nm) was quenched in presence of GNR as gold nanomaterials are known for quenching the emission of fluorophores in close proximity (Fig. 2).5 The blue-shift in emission maxima (almost by 20 nm, from 420 nm to 400 nm) in presence of GNR is likely due to the interaction between GNR and CD. In addition, the TEM images (Fig. 1b-c) show the occurrence of CDs over the GNR surface, which is consistent with the formation of the GNRCD composite. We propose that the electrostatic attractive force between cationic GNR and anionic CDs as well as the hydrophobic attraction of the long carbon chain plays a crucial
2 | Journal Name, [year], [vol], 0000

Fig. 3 Variation in kapp of p-nitrophenol reduction by NaBH4 in presence of GNR-CD nanocomposite in aqueous phosphate buffer (pH 7, 25 mM) at 25 C ([Au] = 50 M in all GNR-CD composite).

75

80

Furthermore, we have also monitored the recyclability of the GNR-CD nanocomposite in catalyzing the reduction. Our experiments showed that the catalytic ability remained about 80% even after completing the fourth reduction cycle (Fig. 4). In fact, the TEM image of the GNR-CD nanocomposite revealed the encirclement of the CD on the GNR surface even after the fourth cycle (Fig. S4, ESI). However, the gradual loss in the catalytic ability might be due to detachment of parts of CD from the GNR
This journal is The Royal Society of Chemistry [year]

ChemComm

Page 4 of 18

10

surface as the number of cycle is increased. This cyclic stability and retainment of the catalytic activity of this nanocomposite is of high significance in terms of its use as a potential catalyst. It is obvious that the presence of CD resulted a 2-fold increase in the catalytic rate of the reduction of p-nitrophenol when combined with GNR, which itself is known as a good catalyst for this reaction.9 This might be due to the acceleration of the electron transport through the graphitic carbonaceous core of the CD. In addition, p-nitrophenol is firmly placed within close proximity of the gold surface aided by the hydrophobic carbon chain of the nanocomposite. In fact, the presence of p-nitrophenol

45

50

55

60

m-dinitrobenzene (244 to 241 nm) in GNR and GNR-CD composite validates the presence of the compound in the hydrophobic domain of the nanocomposite (Fig. S8, ESI). In this case also, the pseudo first order rate constant of the reaction was found to be increased by 2 fold in presence of CD (from 0.14 s-1 to 0.28 s-1) (Fig. S9, ESI). In conclusion, we have developed a new class of GNR-CD nanocomposite which shows high efficiency in catalyzing reduction of different aromatic nitrogroups. We believe the presence of CD increased the rate of electron transfer as well as secures the localization of the reactant molecules within the catalyst, and thus a 2-fold enhancement in catalytic activity in comparison to only GNR was found almost in every case. This novel catalyst is stable in water and has shown good recyclable efficiency towards catalysis. Most interestingly, the catalysis can also be efficiently performed in water-insoluble compound, like m-dinitrobenzene. Importantly, to the best of our knowledge, this is the first report of the catalytic properties of carbon dot in conjugation with GNR, for the reduction of nitroarenes and thus present potential applications in the design of various industrially important catalysts.

Notes and references

65

1. 2.

Fig. 4 Recyclability of the GNR-CD nanocomposite as catalyst for the reduction of p-nitrophenol.

70

3.

15

20

25

30

35

40

in the hydrophobic domain was is consistent with a slight blueshift in UV spectra of the compound in presence of GNR-CD composite in the aqueous buffer (Fig. S5, ESI). Thus, it is likely that an enhanced capacity for transfering electron lead to an increase in catalytic rate of the reduction. However, beyond a certain concentration of the CD in the GNR-CD nanocomposite, the rate of catalysis remained same probably due to the lack of penetration space by the reactant molecules to get close to the GNR surface. To this end, we have also observed the ability of this GNR-CD nanocomposite to catalyze reduction of o-nitrophenol to oaminophenol. The concentration of Au and CD in the nanocomposite were maintained at 50 M and 50 g mL-1. In this case, progress of this pseudo first order reaction was monitored spectrophotometrically by observing the rate of decrease in the absorbance at 420 nm (characteristic UV peak of o-nitrophenol) (Fig. S6, ESI). Here also, the rate of the reduction was increased by 1.6 fold in presence of CD. The observed kapp was 0.064 s-1 in only GNR solution, which increased to 0.104 s-1 in the GNR-CD nanocomposite in aqueous buffer (Fig. S6, ESI). However, in absence of the catalyst almost no reduction occurred. We have also used one water-insoluble substrate (mdinitrobenzene) to check the efficacy of our designed GNR-CD nanocomposite towards its reduction. The m-dinitrobenzene reduced to m-phenylenediamine in presence of NaBH4 and our nanocomposite in aqueous phosphate buffer.14 The corresponding change in UV-vis spectra also delineated this fact (Fig. S7, ESI). In addition, the gradual blue shift in UV-vis spectral maxima of
This journal is The Royal Society of Chemistry [year]

75

4.

5.
80

6.

85

7. 8.
90

9. 10. 11.
95

12. 13.
100

14.

M. Haruta, Catal. Today, 1997, 36, 153. G. A. Somorjai, A. M. Contreras, M. Montano and R. M. Rioux, Proc. Natl. Acad. Sci. USA, 2006, 103, 10577; X. Yuan, G. Sun, H. Asakura, T. Tanaka, X. Chen, Y. Yuan, G. Laurenczy, Y. Kou, P. J. Dyson, N. Yan, Chem. Eur. J., 2013, 19, 1227. M. Boronat and A. Corma, Langmuir, 2010, 26, 16607; A. Jakhmola, R. Bhandari, D. Pacardo and M. R. Knecht, J. Mater. Chem. 2010, 20, 1522; C. Ornelas, J. Ruiz, L. Salmon and D. Astruc, Adv. Synth. Catal., 2008, 350, 837; R. Bhandari and M. R. Knecht, ACS Catal. 2011, 1, 89; V. Polshettiwar, J.-M. Basset, and D. Astruc. ChemSusChem, 2012, 5, 6. J. Zeng, Q. Zhang, J. Chen and Y. Xia, Nano Lett., 2010, 10, 30; J. Lee, J. C. Park, J. U Bang and H. Song, Chem. Mater., 2008, 20, 5839. J. Zhang, G. Chen, M. Chaker, F. Rosei and D. Ma, Appl. Catal. B: Environmental, 2013, 107, 132; S. Maiti, M. Ghosh and P. K. Das, Chem Commun., 2011, 47, 9864. Z. Liu, K. Yang, Y. Liu and S. -T. Lee, J. Mater. Chem., 2012, 22, 24230; J. C. G. E. da Silva and H. M. R. Goncalves, Trends Anal. Chem. 2011, 30, 1327; S. S. Chou, M. De, J. Luo, V. M. Rotello, J. Huang and V. P. Dravid, J. Am. Chem. Soc., 2012, 134, 16725. K. Das, S. Maiti, M. Ghosh, D. Mandal and P. K. Das, J. Colloid Interface Sci., 2013, 395, 111. S. N. Baker and G. A. Baker, Angew. Chem. Int. Ed 2010, 49, 6726; J. C. G. E. da Silva and H. M. R. Goncalves, TrAC, Trends Anal. Chem., 2011, 30, 1327. X. Guo, Q. Zhang, Y. Sun, Q. Zhao and J. Yang, ACS Nano, 2012, 6, 1165. N. R. Jana, Small, 2005, 1, 875. A. B. Bourlinos, A. Stassinopoulos, D. Anglos, R. Zboril, V. Georgakilas and E. P. Giannelis, Chem. Mater., 2008, 20, 4539. P. Herves, M. Perez-Lorenzo, L. M. Liz-Marzan, J. Dzubiella, Y. Lub and M. Ballauff, Chem. Soc. Rev., 2012, 41, 5569. R. Jin, Y. Xing, X. Yu, S. Sun, D. Yu, F. Wang, W. Wu and S. Song, Chem. Asian J., 2012, 7, 2955; S. Rana and K. M. Parida, Catal. Sci. Technol., 2012, 2, 979. A. A. Vernekar, S. Patil, C. Bhat and S. G. Tilve, RSC Adv., 2013, 3, 13243.

Journal Name, [year], [vol], 0000 | 3

Page 5 of 18

ChemComm

Graphical abstract

Gold nanorod-carbon dot nanocomposite was developed which is highly efficient in catalyzing reduction of nitroarenes. Presence of carbon dot on GNR surface enhanced the catalytic rate by two fold.

ChemComm

Page 6 of 18

221x203mm (96 x 96 DPI)

Page 7 of 18

ChemComm

244x203mm (96 x 96 DPI)

ChemComm

Page 8 of 18

224x188mm (150 x 150 DPI)

Page 9 of 18

ChemComm

219x177mm (150 x 150 DPI)

ChemComm

Page 10 of 18

Formation of gold nanorod-carbon dot nanocomposite with superior catalytic ability towards reduction of aromatic nitrogroup in water
Pritiranjan Mondal,a Krishanu Ghosal, a Swarup Krishna Bhattacharyya, a Debabrata Ganguly, a Mithun Das, a Abhijit Bera, a R. K. Gupta, b Angel A. Mart, c Bipin Kumar Gupta* d and Subhabrata Maiti* a Department of Applied Chemistry and Industrial Chemistry, Ramakrishna Mission Vidyamandira, Belurmath, Howrah 711 202, India, E-mail: subhabrata.maiti@gmail.com.
b a

Department of Chemistry, Pittsburg State University, Pittsburg, KS 66762, USA

c

Dept. of Chemistry and Bioengineering, Rice University, Houston, TX 77005

National Physical Laboratory (CSIR) Dr K S Krishnan Road, New Delhi 110012, India ; E-mail:bipinbhu@yahoo.com

Electronic Supplementary Information

Materials and instruments: HAuCl4 (30 wt. %) solution, 11-aminoundecanoic acid were purchased from Sigma, USA. Silver nitrate, citric acid, sodium borohydride, p-nitrophenol, o-nitrophenol, mdinitrobenzene, cetyltrimehylammonium bromide and other reagents were purchased from Merck (India) and were of highest analytical grade. The UV-visible absorption spectra were recorded on a Perkin-Elmer Lambda 25 spectrophotometer. Fluorescence spectra were measured in Varian Cary Eclipse luminescence spectrometer. Zeta potential was recorded in zetasizer Nano-ZS of Malvern instrument limited. Synthesis of gold nanorod: Gold nanorod was formed by following the protocol described elsewhere (reference 10 in the main manuscript). Briefly, 5 mL of aqueous solution of cetyltrimethylammonium bromide (CTAB) was mixed with solution of HAuCl4. The final concentrations of CTAB and HAuCl4

S1

Page 11 of 18

ChemComm

were maintained at 0.1 M and 1 mM, respectively. Then, ascorbic acid and AgNO3 were added in this solution so that the concentration of ascorbic acid and AgNO3 was 2 mM and 0.10 mM. Finally, 50 L of 1mM freshly prepared aqueous NaBH4 solution was added. The colorless solution (yellow to colorless transition occurred upon addition of ascorbic acid) started to appear pink-violet within few min indicating the formation of gold nanorods.

Synthesis of carboxylate functionalized carbon dot (CD): CD was synthesized by following the reported protocol (Reference 11 in the main manuscript). For the synthesis of CD, initially 2 g H2N(CH2)10COOH were added in 25 mL H2O and neutralized by 0.45 g NaOH. The solution was added to 25 mL of an aqueous solution containing 2 g citric acid. The addition of citric acid resulted a thick precipitate after stirring and the precipitate was collected by filtration. It was partially dried overnight at room temperature. This gummy paste was further dried at 85 C for 2 h. The solid was crashed into a fine powder and directly oxidized in air at 300 C for 2 h in a muffle oven. The crude product was extracted with 25 mL of hot water using sonication. The mixture was then centrifuged to remove any insoluble particles and the supernatant aqueous layer was collected. The deep brown supernatant solution was precipitated by centrifuging at 14000 rpm for 1 h after addition of acetone at 1:10 volume ratio. The supernatant was removed and the precipitated brownish black mass was further dried in hot oven at 80 C until it became powder in nature. Catalytic study. In a typical experiment, 2 L of p-nitrophenol/ o-nitrophenol/ mdinitrobenzene stock solution was added into 2.0 mL aqueous buffer of GNR-CD nanoconjugate (of different composition, mentioned in the main manuscript), so that final concentration of the reactant was 0.1 mM. Stock solution of o-nitrophenol, m-dinitrobenzene was made in ethanol. To the mixed solution of catalyst and reactant, 0.1 mL of NaBH4 was added with stirring to start the reaction (final concentration of NaBH4 = 0.1 M). The progress S2

ChemComm

Page 12 of 18

of the reaction was carried out by UV-vis study at ambient temperature (27 C). After the completion of the reaction, the total solution was centrifuged for 60 second to separate the catalyst. It was washed with MilliQ water and then, air dried for further using as catalyst. Calculation of the rate constant. The pseudo-first-order kinetics with respect to the reactants could be applied to our experimental system. The approximately linear shape of the plot of -ln At/A0 (A0 represents the initial and At the absorbance after time t at corresponding wavelength) versus time, as shown in Figure S3. As absorbance is proportional to concentration it corresponds to the concentration of the reactants. From, the slop of the linear equation the apparent rate constant (kapp) is calculated. TEM study: For TEM, a drop of the GNR, CD and GNR-CD nanocomposite solution was cast on 300-mesh Cu-coated TEM grid separately and dried under vacuum for 4 h before taking the image. TEM images were taken on a JEOL JEM 2010 microscope.

S3

Page 13 of 18

ChemComm

Fig. S1 TEM images of a) synthesized GNR, b) anionic carbon dot.

Fig. S2 Time-dependent UV-vis spectra of p-nitrophenol reduction in presence of GNR-CD nanocomposite in aqueous phosphate buffer (pH 7.0, 25 mM) at 25 C.

S4

ChemComm

Page 14 of 18

Fig. S3 a) The change in absorbance of p-nitrophenol with respect to time in presence and absence of catalyst and b) plot of lnAt/A0 against time to find the rate constant for pnitrophenol reduction.

Fig. S4 TEM image of GNR-CD nanocomposite after fourth cycle of p-nitrophenol reduction.

S5

Page 15 of 18

ChemComm

Fig. S5 UV-vis spectra of p-nitrophenol in absence and presence of GNR-CD nanocomposite in aqueous phosphate buffer.

S6

ChemComm

Page 16 of 18

Fig. S6 a) The change in absorbance of o-nitrophenol in presence of the GNR-CD catalyst and b) plot of lnAt/A0 against time to find the rate constant for o-nitrophenol reduction.

S7

Page 17 of 18

ChemComm

Fig. S7 Time-dependent UV-vis spectra of m-dinitrobenzene reduction in presence of GNRCD nanocomposite in aqueous phosphate buffer (pH 7.0, 25 mM) at 25 C.

Fig. S8 UV-vis spectra of m-dinitrobenzene in absence and presence of catalyst in aqueous phosphate buffer.

S8

ChemComm

Page 18 of 18

Fig. S9 Plot of ln At/A0 against time to find the rate constant for m-dinitrobenzene reduction.

S9