Human Hair: A Suitable Platform for Catalytic Nanoparticles - ACS

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Human Hair: A Suitable Platform for Catalytic Nanoparticles Dian Deng, Mayakrishnan Gopiraman, Seong Hun Kim, Ill-Min Chung, and Ick Soo Kim ACS Sustainable Chem. Eng., Just Accepted Manuscript • DOI: 10.1021/ acssuschemeng.6b01689 • Publication Date (Web): 31 Aug 2016 Downloaded from http://pubs.acs.org on September 5, 2016

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ACS Sustainable Chemistry & Engineering

Human Hair: A Suitable Platform for Catalytic Nanoparticles Dian Deng,┴,† Mayakrishnan Gopiraman,*,‡ Seong Hun Kim,§ Ill-Min Chung,┴,‡ and Ick Soo Kim*,†

†

Nano Fusion Technology Research Group, Division of Frontier Fibers, Institute for Fiber

Engineering (IFES), Interdisciplinary Cluster for Cutting Edge Research (ICCER), Shinshu University, Tokida 3-15-1, Ueda, Nagano prefecture, 386-8567, Japan ‡

Department of Applied Bioscience, College of Life & Environment Science, Konkuk

University, 120 Neungdong-ro, Gwangjin-gu, Seoul 05029, South Korea §

Department of Organic and Nano Engineering, Hanyang University, 222 Wangsimni-ro,

Seongdong-gu, Seoul 133-791, South Korea

Corresponding Authors *E-mail: [email protected] (M. Gopiraman).

ACS Paragon Plus Environment


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ABSTRACT: Human hair (HH) has been utilized as a support for Au and Ag nanoparticles (NPs) for the very first time. Initially, a very fine human hair powder (HHP) was obtained from HH by simple ball milling method. The HHP after chemical treatment (e-HHP) was used to prepare two different nanocatalysts, Ag NPs immobilized e-HHP (Ag/HHP) and Au NPs decorated e-HHP (Au/HHP). Influence of e-HHP on the morphology of nanocatalyts and metalsupport interactions were studied. Merit of Ag/HHP and Au/HHP was realized from its excellent yields in cyclo addition and aza-Michale reactions, respectively. Reusability and heterogeneity tests of the nanocatalysts were also performed.

KEYWORDS: human hair, catalyst support, metal nanoparticles, nanocomposite, catalysis, reusable

INTRODUCTION Human hair (HH) is a complex tissue consists of proteins, lipids, water and pigments in which proteins of hard fibrous type known as keratin is largely presented (67-88%).1 Unlike other biomaterials, structural morphology of HH-tissue is highly unique and it is nearly impossible to mimic the structure. HH-derived biomaterials have been employed in biomedical applications.2 Walter et al.,3 utilized HH fiber as a reactor/medium for the controlled synthesis of fluorescent Ag nanoparticles. PbS nanocrystals were also formed within the HH-matrix during blacking.4 They found that the shape and distribution of nanoparticles are controllable. In spite of these advantages and availability, the HH is often considered as biowaste.5 Proteins in HH are heteroatom (O, N and S) rich condensation polymers of amino acid. Chemical and physical integrity of the HH units are extremely good respectively due to the presence of cystine group (-


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s-s- bonds) and cortex.6 In addition, the keratin of HH is one of the highly insoluble fibrousproteins in most of the organic solvents.1-6 Fiber structure and the presence of heteroatom is also interesting points to be noted. Considering its unique physical and chemical properties, we assumed that the human hair would be a suitable candidate for the immobilization of catalytic metal nanoparticles (NPs). Besides, we expected that HH would overcome the drawbacks of common supports (silica, alumina, carbon materials and polymers). In general, the catalyst support provides a platform for NPs to have a much larger number of active atoms at the surface.7 Nanocellulose,8 wool-keratine,9 chitosan,10 natural pumice,11 mycelial,12 gram negative bacteria, and gram positive bacteria13 are some of the green supports reported to date. However, most of the common supports are moderately expensive, difficult to prepare, toxic and environmentally non-friendly. In addition, hydrophobic nature of the common supports (carbon nanomaterials including biomass-derived activated carbons) often limits metal-support interaction which leads the further growth and aggregation of NPs.14,15 To overcome this issue, additional surface modifications are necessary for the supports prior to the immobilization of NPs.16 Moreover, to control the NPs size and morphology of catalysts, surfactants are often used.17 Expensive and hazardous acid treatments (H2SO4/HNO3 or HCl) have being performed for carbon materials to make them suitable as support for decoration of metal NPs.18 Similarly, the surface of cellulose nanofiber was modified with anionic groups to obtain better morphology of NPs-supported cellulose catalysts.19 Notably, obtaining better morphology of green catalysts at high metal loading is also highly challenging task.20,21 Considerable effort has been devoted to develop green and sustainable protocols for the preparation of nanomaterials by R. S. Varma.22,23 According to Joo et al.,24 a good support must have strong interaction with foreign elements and, have strong influence on the morphology and better activity of the targeted composites. Noble



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metals including Au and Ag are generally inactive in the bulk form, whereas, the Au and Ag NPs with diameter of few nanometers are highly efficient. In addition, synergistic effects between metals (Au or Ag NPs and other foreign metals) may also improve the activity of Au and Ag NPs. We believe that the polymetallic nature of HH would enhance the activity of Ag and Au NPs. To our delight, this is the first investigation on human hair-supported Au and Ag catalysts reported for organic transformations.

RESULTS AND DISCUSSION Initially, virgin human hair (HH) was ball milled to obtain fine powder (HHP). Readily leachable constituents present in HHP were removed by modified-Shindai method and e-HHP was obtained.5 Then, the e-HHP was dispersed in 50 mL of aqueous solution containing 31.5 mg of AgNO3 and magnetically stirred under open air atmosphere at 60°C for 24 h. Subsequently, the AgNO3 was reduced to metallic Ag NPs by a drop wise addition of aqueous NaBH4 solution. Finally, the solid nanocatalyst (Ag/HHP) was filtered out and vacuum dried. Similarly, HAuCl3.xH2O (34.5 mg) was used to obtain Au/HHP. HRTEM images of Ag/HHP and Au/HHP are presented in Figure 1. Successful decoration of NPs on e-HHP surface was confirmed. The Au and Ag NPs were spherical in shape, uniformly dispersed and very small with narrow particle size distribution (Figure 1d and 1h). The average diameter of Ag and Au NPs was calculated to be 3.1 and 3.4 nm, respectively. The strong affinity between metal ions and e-HHP might have controlled the growth of NPs during the reduction process of metal salts by NaBH4. At some places, moderately big particles were also seen in both the cases (Figures S1 & S2 in Supporting Information). To observe HRTEM images, nanocatalysts were dispersed in organic solvent followed by sonication and


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vigorous stirring. Despite of that, background of the HRTEM images was very clear which notices 100% utilization of NPs by e-HHP. In addition, the result strongly supports the better adhesion of NPs with e-HHP. SEM-EDS and corresponding elemental mappings are provided in Figure 2. Five different places were chosen to record the SEM-EDS for both samples and average wt% of Au and Ag was calculated (Figures S3 & S4 in Supporting Information). The average wt% of Ag in Ag/HHP and Au in Au/HHP was calculated to be 8.6 and 21.1, respectively. The EDS spectra confirmed the presence of C, O, N, Mg, Al, Si, S, and Fe elements in both Au/HHP and Ag/HHP (Figures S3 & S4 in Supporting Information). EDS-elemental mappings revealed the homogeneous distribution of Au and Ag on e-HHP (data not shown). Since the surface area and textural properties of catalyst are very important, BET analysis was carried out for e-HHP, Ag/HHP and Au/HHP. The BET specific surface area of 52.73 m2/g with good pore volume (Vp, 0.1881 cm3/g) and average pore size (dp, 14.26 nm) was determined for eHHP. After metal loading, the BET surface area of e-HHP was found to be slightly decreased. A maximum surface area of 35.43 m2/g (with Vp = 0.152 cm3/g, and dp = 11.56 nm) and 43.59 m2/g (with Vp = 0.1645 cm3/g, and dp = 12.76 nm) was found out for Ag/HHP and Au/HHP, respectively. Figure 3 demonstrates the XRD patterns of e-HHP, Ag/HHP and Au/HHP. For all the three samples, a broad and intense peak at 2θ = 23° was noticed. In addition, two sharp peaks at 2θ= 26.3° and 27.5° were observed. These peaks may be attributed to the structural fibrous proteins which show the e-HHP consists of both crystalline and amorphous parts. Typical XRD pattern of Ag/HHP showed Bragg reflections with 2θ values of 38.03°, 46.18°, 63.43° and 77.18° correspond to (1 1 1), (2 0 0), (2 2 0) and (3 1 1) facets respectively, indicating facecentered cubic (fcc) Ag in metallic form (JCPDS File No. 87-0720).21 Alike, four new peaks at



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2θ = 38.2, 44.4, 64.6 and 77.6, which can be indexed to (111), (200), (220), (311) and (222) planes of metallic Au. The data shows that Au NPs is crystalline with (fcc) packing arrangement of bulk Au (JCPDS file No. 04-0784).25 After immobilization of NPs, the peak intensity at 2θ = 23° slightly reduced but the intensity and shape of the sharp peaks at 2θ= 26.3° and 27.5° were maintained. The findings reveal that metal NPs were attached mostly on the surface of e-HHP and the inner cores of e-HHP were sustained. Chemical state of e-HHP, Ag/HHP and Au/HHP were investigated by XPS analysis (Figures 4, 5 & S5, Supporting Information). Four intense XPS peaks at 282.5 (C 1s), 529.5 (O 1s), 397.8 (N 1s) and 162.2 (S 2p) eV were noticed for all three samples. In addition, binding energies corresponding to Al (130.5 eV, Al 2s), Fe (737. 2 eV, Fe 2p3/2) and Si (120 eV, Si 2p) were also clearly seen. These results demonstrate the polymetallic nature of the catalysts (Ag/HHP and Au/HHP) which is an extra credit when taking human hair as a support. Biomassderived nanomaterials have recently attracted much interest in various fields including catalysis owing to their polymetallic nature.26 In fact, polymetallic nature of the present Au/HHP and Ag/HHP would improve the catalytic performance by involving synergetic effect between NPs and other elements accommodated in e-HHP.26 In case of Ag/HHP, XPS spectrum showed two intense peaks at 366.5 eV (Ag 3d3/2) and 372.5 eV (Ag 3d5/2). In comparison to metallic Ag 368.1 eV (Ag 3d3/2) and 374.1 eV (Ag 3d5/2), the binding energies of Ag 3d shifted towards lower binding energies by ~2 eV with Ag 3d doublet slitting of 6.0 eV, indicating metallic nature of Ag in Ag/HHP.27 Similarly, in the 4f region, a doublet 4f7/2 (86.2 eV) and 4f5/2 (82.5 eV) was noticed for Au/HHP. This doublet was observed to be shifted towards positive side by 2.2 eV compared to Au 4f7/2 peak of metallic Au (84.0 eV).28 Moreover, after metal loading, the XPS peaks (C 1s, O 1s, N 1s and S 2p) were observed to be shifted significantly towards higher


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binding energies and the intensity of these peaks decreased as well (Figure 4) which mainly due to (a) charge transfer between NPs and O, N, S-groups of e-HHP, (b) synergetic effect by metalmetal interaction, (c) immobilization of NPs mostly on the surface of e-HHP, and (d) better metal-support interaction.29 These findings are in good agreement with the HRTEM, XRD and SEM-EDS results. In general, keratin often suffers from poor processability due to inert and insoluble nature.30 However, the keratin can be turned to be a processable material via chemical treatment by slightly affecting the inactive functional bonds such as -s-s- bonds. Particularly, the extraction procedures have huge influence on the physicochemical properties of the keratin-rich biomass materials.30,31 In the present case, the chemical treatment would have assisted the HH (including keratin) to be a suitable catalyst platform. As a result, good attachment between NPs and e-HHP was obtained. As expected, the Ag/HHP and Au/HHP demonstrated an excellent catalytic activity in aza-Michael and 1,3-dipolar cycloaddition reactions, respectively (Schemes 1 & 2). Both these reactions are very important in organic synthesis since the catalytic systems afford high-value products of fine chemical and pharmaceuticals. Optimal reaction conditions were found out for both Ag/HHP and Au/HHP systems (data not shown). Due to the interesting elemental composition of e-HHP (refer EDX and XPS data), a blank reaction with only e-HHP (without metal loading) was carried out. However, the reaction was very slow and the reaction did not achieve the maximum yield even after prolonged reaction time. The Ag NPs with very small in size (~2.5 nm) can easily activate the C-C double bonds and promote the rate of the reactions. To our delight, a very low amount of 2 mg of Ag/HHP (0.16 mol% of Ag) could be sufficient for the reaction. Under optimized conditions, Ag/HHP gave methyl 3-(piperidin-1-yl)propanoate (2a) in excellent yield (>99%) with 100% selectivity from the reaction of piperidine (1a) and methyl



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acrylate (1b). The present system showed a better TON/TOF value of 619/2475 h-1 compared to Au/TiO2.32 Similarly, Ag/HHP mediated aza-addition of 1a and acrylonitrile (1c) afford 3(piperidin-1-yl)propanenitrile (2b) in excellent >99% yield (100% selectivity) and the TON/TOF was found to be very high (619/2475 h-1). Generally, Au catalysts are one of the best activators of unsaturated carbon-carbon bonds (activation via nucleophilic attack on the multiple bonds). Worth to mention that 0.21 mol% of Au (2 mg of Ag/HHP) was sufficient for the reaction. Moreover, the reactions were performed in water at reflux condition. A better 91% yield of 1benzyl-4-phenyl-1H-1,2,3-triazole (4a) with excellent TON/TOF (433/217 h-1) was obtained from Au/HHP-medicated cycloaddition of ethynylbenzene (3a) and (azidomethyl)benzene (3b). Alike, reaction of 1-ethynyl-4-methylbenzene (3c) with 3b transformed to 1-benzyl-4-(p-tolyl)1H-1,2,3-triazole (4b) in excellent 95% yield with very high TON/TOF of 452/226 h-1. The performance of Ag/HHP and Au/HHP can be compared with other NPs-supported catalysts including Au/TiO2,32 CuO/GNS,33 [CuBr(PPh3)3],34 copper(I),35 GNS,36 Cu NPs.37 There are mainly five obvious reasons for the excellent catalytic activity of Ag/HHP and Au/HHP; (1) high surface area, (2) very small NPs, (3) metal-support interaction, (4) synergetic effect between NPs and other elements (Fe, Al and Mg) present in the human hair, and (5) good dispersion of nanocatalysts in reaction medium. To further, heterogeneity and reusability of Ag/HHP and Au/HHP were studied. After the reaction complete, the reaction mixture was centrifuged to separate the catalyst and the filtrate was analyzed by ICP-MS. The results confirmed that there is no metal leaching from the catalysts during the reaction, indicating true heterogeneous nature of the catalysts. It was found that the catalysts can be reused for at least four cycles without significant loss in the activity. At 4th cycle, the Ag/HHP afforded 99% of methyl 3-(piperidin-1-yl)propanoate (2a) with high


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TON/TOF (619/2475 h-1) and selectivity (100%). In case of Au/HHP system, 80% of 1-benzyl4-(p-tolyl)-1H-1,2,3-triazole (4a) was obtained at 4th cycle. The TON/TOF and selectivity were calculated to be 380/191 h-1 and 100% respectively.

CONCLUSION Herein, we conclude that human hair (e-HHP) can be an efficient support for catalytic metal NPs. Physicochemical properties and catalytic activity of the present Ag/HHP and Au/HHP were found to be excellent. The catalysts (Ag/HHP and Au/HHP) are reusable and heterogeneous in nature. Loading of metal on e-HHP can be easily controlled. Interestingly, better morphology of catalysts even with higher metal loadings was also proved. We believe that the present results would open a new door for human hair-based nanocomposites (including other keratin rich biomass materials like wool) in various fields including nanoscience and catalysis.

EXPERIMENTAL SECTION Materials and Characterization Raw human hair was obtained from salon shop in Nagano, Japan. All other chemicals were delivered by Sigma Aldrich or Wako Pure Chemicals and used as received. The structural morphology of Ag/HHP and Au/HHP was investigated on a JEOL JEM-2100F TEM. The accelerating voltage of 120 kV was fixed. To find out the wt% of Au in Au/HHP and Ag in Ag/e-HHP, SEM images, EDS spectra and corresponding X-ray elemental maps were recorded using Hitachi 3000H SEM. XPS (Kratos Axis-Ultra DLD, Kratos Analytical Ltd, Japan) was recorded to study the chemical state of Ag/HHP and Au/HHP. During the XPS analysis, the Ag/HHP and Au/HHP were irradiated with Mg Kα ray source. X-ray diffraction patterns (XRD)



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were recorded using Rotaflex RTP300 Diffractometer (Rigaku Co., Japan) with nickel-filtered Cu ka radiation. An applied current of 200 mA and the accelerating voltage of 40 kV were adopted.

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C NMR (100 MHz) and 1H NMR (400 MHz) spectra were recorded on Bruker

spectrometer. Dimethyl sulfoxide (DMSO-d6) and tetramethylsilane (TMS) were used as solvent and internal reference, respectively. ImageJ software was used to determine the particle size of MNPs. The specific surface area of Ag/HHP and Au/HHP was calculated using BrunauerEmmett-Teller (BET) method [TriStar 3000 (Micromeritics, USA)]. The leaching property was verified using inductively coupled plasma-mass spectrometer (ICP-MS, 7500CS, Agilent). The catalytic activity of Ag/HHP and Au/HHP was investigated using Shimadzu-2010 gas chromatograph (GC). The GC was equipped with Restek-5 capillary column (5% diphenyl and 95% dimethyl siloxane, 0.32 mm dia, 60 m in length) and a flame ionization detector (FID). N2 was used as a carrier gas. The initial column temperature was increased from 60 to 150°C at the rate of 10°C/min and then to 220°C at the rate of 40°C/min. The temperatures of the FID and injection port were kept constant at 150 and 250°C, respectively. Yield of the catalytic product, conversion and selectivity were calculated by using the equations (1), (2) and (3), respectively. Equations 4 and 5 were used to measure the turn over number (TON) and turn over frequency (TOF), respectively. GC yield (%) = % of product formed

(1)

GC conversion (%) = 100 – % of reactant remains

(2)

Selectivity (%) = 100 – (conversion – yield)

(3)

TON = the amount of product (mol)/the amount of active sites

(4)

TOF = TON/time (h)

(5)


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For all the catalytic reactions, the products and unconverted reactants were analyzed by GC. After removing Ag/HHP and Au/HHP, the reaction mixture was diluted with ethyl acetate and dried over anhydrous MgSO4. Subsequently, the ethyl acetate was evaporated using rotary evaporator and the catalytic products were isolated using silica column. 1H and 13C NMR spectra were taken to identify the catalytic products.

Preparation of e-HHP A ~5 g of HH used to obtain a fine human hair powder (HHP) by ball milling method. The HHP was washed well with distilled water and then vacuum dried. Then the HHP was washed with ethanol and then stirred in a mixture of chloroform/methanol (2:1, v/v) for 3 days at 50°C to remove the lipids and dyes present in the HHP. The resultant powder was mixed with a 75 mL solution containing 25 mM Tris–HCl, pH 8.5, 2.6 M thiourea, 5 M urea and 5% 2mercaptoethanol at 50°C for 24 h. The mixture was filtered and centrifuged at 25°C. Finally, the resultant solid (e-HHP) was used as a support for the decoration of Au and Ag NPs.

Preparation of Ag/HHP and Au/HHP A mixture of e-HHP (250 mg), AgNO3 (31.5 mg) and water (50 mL) was magnetically stirred under atmospheric pressure of air at 60°C for 24 h. Subsequently, aqueous NaBH4 solution was slowly added to the above mixture to reduce the AgNO3. Finally, the resultant solid (Ag/HHP) was filtered out and vacuum dried. Similarly, HAuCl3.xH2O (34.5 mg) was used to obtain Au/HHP.



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Procedure for aza-Michael reaction by Ag/HHP A mixture of piperidine (1a, 2 mmol), methyl acrylate (1b, 2 mmol) and Ag/HHP (2 mg, 0.16 mol%) was magnetically stirred under open air atmosphere at 25°C for 15 min. After the reaction complete, Ag/HHP was separated by a simple centrifuging method and product was isolated and confirmed by GC and NMR.

Procedure for 1,3-dipolar cycloaddition catalyzed by Au/HHP 2 mg of Au/HHP (0.21 mol%), 1 mmol of ethynylbenzene (3a), 1 mmol of (azidomethyl)benzene (3b) and 1 mL of water were magnetically stirred at 100°C for 2 h. After the reaction complete, Ag/HHP was separated by a simple centrifuging method and product was isolated and confirmed by GC and NMR. 1-benzyl-4-phenyl-1H-1,2,3-triazole (4c): 1H NMR (400 MHz, DMSO-d6): δ 5.70 (2, 2H), 7.26-7.46 (m, 8H), 7.94-8.01 (m, 2H), 8.67 (s, 1H) ppm;

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C NMR (100 MHz, DMSO-d6): δ

53.5, 125.6, 127.5, 127.7, 128.2, 129.1, 129.2, 129.3, 129.7, 147.2 ppm. 1-benzyl-4-p-tolyl-1H-1,2,3-triazole (4d): 1H NMR (400 MHz, DMSO-d6): δ 2.34 (s, 3H), 5.63-5.67 (d, 2H), 7.00-7.42 (m, 7H), 7.72-7.74 (m, 2H), 7.92 (s, 1H) ppm; 13C NMR (100 MHz, DMSO-d6): δ 21.8, 53.3, 125.4, 127.1, 129.0, 129.1, 129.2, 129.7, 129.9, 136.4, 134.2, 145.4 ppm.

ASSOCIATED CONTENT Supporting Information The Supporting Information is available free of charge on the ACS Publications website at DOI: xx.xxxx/acsnano.xxxxxxx.


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TEM, SEM-EDS, XPS, GC chromatogram, 1H and 13C NMR spectra are provided.

AUTHOR INFORMATION Corresponding Authors *E-mail: [email protected] (M. Gopiraman). *E-mail: [email protected] (I.S. Kim).

Authors Contributions ┴Dian Deng and Ill-Min Chung contributed equally to this work and should be considered as cofirst authors.

Notes The authors declare no competing financial interest.

ACKNOWLEDGMENTS This study was supported by Konkuk University KU research professor program.

REFERENCES (1) Clay, R.; Cook, K.; Routh, J.Studies in the Composition of Human Hair. J. Am. Chem. Soc. 1940, 62, 2709-2710. (2) Lee, H.; Noh, K.; Lee, S.; Kwon, I.; Han, D.; Lee, I.; Hwang, Y. Human Hair Keratin and itsbased Biomaterials for Biomedical Applications. Tissue. Eng. Regen. Med., 2014, 11, 255-265. (3) Haveli, S. D.; Walter, P.; Patriarche, G.; Ayache, J.; Castaing, J.; Elslande, E. V.; Tsoucaris, G.; Wang, P. A.; Kagan, H. B. Hair Fiber as a Nanoreactor in Controlled Synthesis of Fluorescent Gold Nanoparticles, Nano Lett., 2012, 12, 6212–6217.



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(4) Walter, P.; Welcomme, E.; Hallegot, P.; Zaluzec, N. J.; Deeb, C.; Castaing, J.; Veyssiere, P.; Breniaux, R.; Leveque, J. L.; Tsoucaris, G. Early Use of PbS Nanotechnology for an Ancient Hair Dyeing Formula, Nano Lett., 2006, 6, 2215–2219. (5) Nakamura, A.; Arimoto, M.; Takeuchi, K.; Fujii, T. A Rapid Extraction Procedure of Human Hair Proteins and Identification of Phosphorylated Species. Biol. Pharm. Bull. 2002, 25, 569572. (6) Kumar, S.; Bhattacharyya, J.; Vaidya, A.; Chakrabarti, T.; Devotta, S.; Akolkar, A. Assessment of the Status of Municipal Solid Waste Management in Metro Cities, State Capitals, Class I Cities, and Class II Towns in India: An Insight. Waste. Manag., 2009, 29, 883895. (7) Tsang, S.; Caps, V.; Paraskevas, I.; Chadwick, D.; Thompsett, D. Magnetically Separable, Carbon-Supported Nanocatalysts for the Manufacture of Fine Chemicals. Angewandte Chemie, 2004, 116, 5763-5767. (8) Kaushik, M. A. Moores, Review: Nanocelluloses as Versatile Supports for Metal Nanoparticles and their Applications in Catalysis, Green Chem., 2016, 18, 622–637. (9) Lu, X.; Cui, S. Wool Keratin-Stabilized Silver Nanoparticles, Bioresource Technol., 2010, 101, 4703–4707. (10) Nasir Baig, R. B.; Nadagouda, M. N.; Varma, R. S. Ruthenium on Chitosan: A Recyclable Heterogeneous Catalyst for Aqueous Hydration of Nitriles to Amides, Green Chem., 2014, 16, 2122–2127. (11) Brito, A.; Garcia, F.; Alvarez, C.; Arvelo, R.; Fierro, J. L. G.; Diaz, C. High Surface Area Support/Catalyst Derived from Natural Pumice. Study of Pretreatment Variables, Ind. Eng. Chem. Res., 2004, 43, 1659–1664.


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Scheme 1. Ag/HHP catalyzed aza-Michael.

+

3b

3a

+

3c

N N N

N3 Au/HHP

4a N N N

N3 4b

3b

Scheme 2. Au/HHP catalyzed [3+2] cycloaddition reaction.

Figure 1 High resolution TEM images of (a, b and c) Ag/HHP and (d, e and f) Au/HHP; inserts shows magnified single corresponding NPs (d, h: histograms showing particle size distribution of Ag and Au NPs, calculated using ImageJ).


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Figure 2 EDS spectra of (a) Ag/HHP and (b) Au/HHP. Inserts shows the corresponding SEM images of (a-1) Ag/HHP and (b-1) Au/HHP.

Figure 3. XRD patterns of HHP, Ag/HHP and Au/HHP.



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Figure 4. XPS (a) C 1s, (b) N 1s, (c) O 1s, (d) S 2p, (e) Si 2p, Al 2p and Al 2s, and (f) Fe 2p peaks of e-HHP (1), Ag/HHP (2) and Au/HHP (3).

Figure 5. XPS (a) Ag 3d and (b) Au 4f peaks.


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For Table of Content Use Only:

Human Hair: A Suitable Platform for Catalytic Nanoparticles Dian Deng,┴,† Mayakrishnan Gopiraman,*,‡ Seong Hun Kim,§ Ill-Min Chung,┴,‡ and Ick Soo Kim*,†

Synopsis: Human hair supported Ag and Au nanoparticles as highly efficient and sustainable nanocatalysts for aza-Michael and [3+2] cycloaddition reactions.



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Human hair supported nanoparticle catalysts Graphical Abstract 254x190mm (96 x 96 DPI)


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Human Hair: A Suitable Platform for Catalytic Nanoparticles - ACS

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