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Nitrogen-doped carbon black supported NiCo2S4 catalyst for hydrogenation of nitrophenols under mild conditions

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Abstract

Catalytic hydrogenation of nitrophenols to aminophenols was considered as the most efficient way to solve their contamination together with huge economic benefit. NiCo2S4 can be used not only as supercapacitor materials, but also competitive catalytic materials in hydrogenation reactions. In this work, a nitrogen-doped carbon black (NCB) supported NiCo2S4 catalyst is successfully prepared by a facile one-pot solvothermal approach. TEM results show that the ultrafine NiCo2S4 particles are uniformly dispersed on the surface of NCB at a low NiCo2S4 loading, while aggregation may occur in NiCo2S4/NCB catalysts with an excessive NiCo2S4 content. The NiCo2S4-30/NCB catalyst with a BET surface area of 47.20 m2 g−1 exhibits the most excellent catalytic activity and durability for heterogeneous catalytic hydrogenation of nitrophenols using NaBH4 as the reducing agent at 30 °C in the aqueous solution. The kinetic constant of hydrogenation of p-nitrophenol catalyzed by NiCo2S4-30/NCB is almost five times higher than the reaction catalyzed by pristine NiCo2S4. The outstanding performance of NiCo2S4-30/NCB is ascribed to the unique nanostructure of the catalyst and the combined effect between the NiCo2S4 and NCB, including abundant surface functional groups of NCB for anchoring and dispersing NiCo2S4, strong adsorption ability for nitrophenol molecules facilitated by π–π stacking interaction, as well as fast electron transfer from NCB to NiCo2S4, resulting in higher local electron densities and thus facilitating the uptake of electrons by nitrophenols.

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References

  1. Dong Z, Le X, Dong C, Zhang W, Li X, Ma J (2015) Ni@Pd core-shell nanoparticles modified fibrous silica nanospheres as highly efficient and recoverable catalyst for reduction of 4-nitrophenol and hydrodechlorination of 4-chlorophenol. Appl Catal B 162:372–380

    Article  Google Scholar 

  2. Feng J, Su L, Ma Y, Ren C, Guo Q, Chen X (2013) CuFe2O4 magnetic nanoparticles: a simple and efficient catalyst for the reduction of nitrophenol. Chem Eng J 221:16–24

    Article  Google Scholar 

  3. Guo P, Tang L, Tang J, Zeng G, Huang B, Dong H, Zhang Y, Zhou Y, Deng Y, Ma L, Tan S (2016) Catalytic reduction–adsorption for removal of p-nitrophenol and its conversion p-aminophenol from water by gold nanoparticles supported on oxidized mesoporous carbon. J Colloid Interface Sci 469:78–85

    Article  Google Scholar 

  4. Hasan Z, Cho D-W, Chon C-M, Yoon K, Song H (2016) Reduction of p-nitrophenol by magnetic Co-carbon composites derived from metal organic frameworks. Chem Eng J 298:183–190

    Article  Google Scholar 

  5. Xia J, He G, Zhang L, Sun X, Wang X (2016) Hydrogenation of nitrophenols catalyzed by carbon black-supported nickel nanoparticles under mild conditions. Appl Catal B 180:408–415

    Article  Google Scholar 

  6. Guo M, He J, Li Y, Ma S, Sun X (2016) One-step synthesis of hollow porous gold nanoparticles with tunable particle size for the reduction of 4-nitrophenol. J Hazard Mater 310:89–97

    Article  Google Scholar 

  7. Liu L, Chen R, Liu W, Wu J, Gao D (2016) Catalytic reduction of 4-nitrophenol over Ni–Pd nanodimers supported on nitrogen-doped reduced graphene oxide. J Hazard Mater 320:96–104

    Article  Google Scholar 

  8. Liu K, Wang Y, Chen P, Zhong W, Liu Q, Li M, Wang Y, Wang W, Lu Z, Wang D (2016) Noncrystalline nickel phosphide decorated poly(vinyl alcohol-co-ethylene) nanofibrous membrane for catalytic hydrogenation of p-nitrophenol. Appl Catal B 196:223–231

    Article  Google Scholar 

  9. Wu YG, Wen M, Wu QS, Fang H (2014) Ni/graphene nanostructure and its electron-enhanced catalytic action for hydrogenation reaction of nitrophenol. J Phys Chem C 118:6307–6313

    Article  Google Scholar 

  10. Jiang Z, Xie J, Jiang D, Wei X, Chen M (2013) Modifiers-assisted formation of nickel nanoparticles and their catalytic application to p-nitrophenol reduction. CrystEngComm 15(3):560–569

    Article  Google Scholar 

  11. Song P, He L-L, Wang A-J, Mei L-P, Zhong S-X, Chen J-R, Feng J-J (2015) Surfactant-free synthesis of reduced graphene oxide supported porous PtAu alloyed nanoflowers with improved catalytic activity. J Mater Chem A 3(10):5321–5327

    Article  Google Scholar 

  12. Zhang L, Jiang X, Shen J, Xu K, Li J, Sun X, Han W, Wang L (2016) Enhanced bioelectrochemical reduction of p-nitrophenols in the cathode of self-driven microbial fuel cells. RSC Adv 6(35):29072–29079

    Article  Google Scholar 

  13. Ma H, Wang H, Wu T, Na C (2016) Highly active layered double hydroxide-derived cobalt nano-catalysts for p-nitrophenol reduction. Appl Catal B 180:471–479

    Article  Google Scholar 

  14. Ndokoye P, Zhao Q, Li X, Li T, Tade MO, Wang S (2016) Branch number matters: promoting catalytic reduction of 4-nitrophenol over gold nanostars by raising the number of branches and coating with mesoporous SiO2. J Colloid Interface Sci 477:1–7

    Article  Google Scholar 

  15. Zhang J, Chen G, Guay D, Chaker M, Ma D (2014) Highly active PtAu alloy nanoparticle catalysts for the reduction of 4-nitrophenol. Nanoscale 6(4):2125–2130

    Article  Google Scholar 

  16. Zhang S, Gai S, He F, Ding S, Li L, Yang P (2014) In situ assembly of well-dispersed Ni nanoparticles on silica nanotubes and excellent catalytic activity in 4-nitrophenol reduction. Nanoscale 6(19):11181–11188

    Article  Google Scholar 

  17. Sadiq Mohamed MJ, Bhat Denthaje K (2016) Novel RGO–ZnWO4–Fe3O4 nanocomposite as an efficient catalyst for rapid reduction of 4-nitrophenol to 4-aminophenol. Ind Eng Chem Res 55(27):7267–7272

    Article  Google Scholar 

  18. He X, Liu Z, Fan F, Qiang S, Cheng L (2015) Preparation of palladium/polyelectrolyte hollow nanospheres and their catalytic activity in 4-nitrophenol reduction. Chin J Appl Chem 32(2):310–316

    Google Scholar 

  19. Morales MV, Rocha M, Freire C, Asedegbega-Nieto E, Gallegos-Suarez E, Rodríguez-Ramos I, Guerrero-Ruiz A (2017) Development of highly efficient Cu versus Pd catalysts supported on graphitic carbon materials for the reduction of 4-nitrophenol to 4-aminophenol at room temperature. Carbon 111:150–161

    Article  Google Scholar 

  20. Shen W, Qu Y, Pei X, Li S, You S, Wang J, Zhang Z, Zhou J (2017) Catalytic reduction of 4-nitrophenol using gold nanoparticles biosynthesized by cell-free extracts of Aspergillus sp. WL-Au. J Hazard Mater 321:299–306

    Article  Google Scholar 

  21. Yang JM, Lu J (2002) Hydrogenation of aromatic ring and nitrobenzene over the amorphous nickel boron alloy. Chin J Appl Chem 19(22):1200–1202

    Google Scholar 

  22. Rana S, Jonnalagadda SB (2017) A facile synthesis of Cu–Ni bimetallic nanoparticle supported organo functionalized graphene oxide as a catalyst for selective hydrogenation of p-nitrophenol and cinnamaldehyde. RSC Adv 7:2869–2879

    Article  Google Scholar 

  23. Shen Y-Y, Sun Y, Zhou L-N, Li Y-J, Yeung ES (2014) Synthesis of ultrathin PtPdBi nanowire and its enhanced catalytic activity towards p-nitrophenol reduction. J Mater Chem A 2:2977–2984

    Article  Google Scholar 

  24. Varadwaj GBB, Oyetade OA, Rana S, Martincigh BS, Jonnalagadda SB, Nyamori VO (2017) Facile synthesis of three-dimensional Mg–Al layered double hydroxide/partially reduced graphene oxide nanocomposites for the effective removal of Pb2+ from aqueous solution. ACS Appl Mater Interfaces 9:17290–17305

    Article  Google Scholar 

  25. Varadwaj GBB, Nyamori VO (2016) Layered double hydroxide- and graphene-based hierarchical nanocomposites: synthetic strategies and promising applications in energy conversion and conservation. Nano Res 9(12):3598–3621

    Article  Google Scholar 

  26. Cai D, Wang D, Wang C, Liu B, Wang L, Liu Y, Li Q, Wang T (2015) Construction of desirable NiCo2S4 nanotube arrays on nickel foam substrate for pseudocapacitors with enhanced performance. Electrochim Acta 151:35–41

    Article  Google Scholar 

  27. Wang J-G, Jin D, Zhou R, Shen C, Xie K, Wei B (2016) One-step synthesis of NiCo2S4 ultrathin nanosheets on conductive substrates as advanced electrodes for high-efficient energy storage. J Power Sources 306:100–106

    Article  Google Scholar 

  28. Zhu T, Wang J, Ho GW (2015) Self-supported yolk-shell nanocolloids towards high capacitance and excellent cycling performance. Nano Energy 18:273–282

    Article  Google Scholar 

  29. Zou R, Zhang Z, Yuen MF, Sun M, Hu J, Lee CS, Zhang W (2015) Three-dimensional-networked NiCo2S4 nanosheet array/carbon cloth anodes for high-performance lithium-ion batteries. NPG Asia Mater 7(6):e195

    Article  Google Scholar 

  30. Ma L, Hu Y, Chen R, Zhu G, Chen T, Lv H, Wang Y, Liang J, Liu H, Yan C, Zhu H, Tie Z, Jin Z, Liu J (2016) Self-assembled ultrathin NiCo2S4 nanoflakes grown on Ni foam as high-performance flexible electrodes for hydrogen evolution reaction in alkaline solution. Nano Energy 24:139–147

    Article  Google Scholar 

  31. Shen L, Wang J, Xu G, Li H, Dou H, Zhang X (2015) NiCo2S4 nanosheets grown on nitrogen-doped carbon foams as an advanced electrode for supercapacitors. Adv Energy Mater 5:1400977

    Article  Google Scholar 

  32. Gao Y, Mi L, Wei W, Cui S, Zheng Z, Hou H, Chen W (2015) Double metal ions synergistic effect in hierarchical multiple sulfide microflowers for enhanced supercapacitor performance. ACS Appl Mater Interfaces 7(7):4311–4319

    Article  Google Scholar 

  33. Xiao Y, Lei Y, Zheng B, Gu L, Wang Y, Xiao D (2015) Rapid microwave-assisted fabrication of 3D cauliflower-like NiCo2S4 architectures for asymmetric supercapacitors. RSC Adv 5(28):21604–21613

    Article  Google Scholar 

  34. Xia C, Li P, Gandi AN, Schwingenschlögl U, Alshareef HN (2015) Is NiCo2S4 really a semiconductor? Chem Mater 27(19):6482–6485

    Article  Google Scholar 

  35. Gao Y-P, Huang K-J (2017) NiCo2S4 materials for supercapacitor applications. Chem Asian J 12:1969–1984

    Article  Google Scholar 

  36. Zhu Y, Wu Z, Jing M, Yang X, Song W, Ji X (2015) Mesoporous NiCo2S4 nanoparticles as high-performance electrode materials for supercapacitors. J Power Sources 273:584–590

    Article  Google Scholar 

  37. Xia J, Fu Y, He G, Sun X, Wang X (2017) Core-shell-like Ni–Pd nanoparticles supported on carbon black as a magnetically separable catalyst for green Suzuki-Miyaura coupling reactions. Appl Catal B 200:39–46

    Article  Google Scholar 

  38. He H, Zhong M, Konkolewicz D, Yacatto K, Rappold T, Sugar G, David NE, Matyjaszewski K (2013) Carbon black functionalized with hyperbranched polymers: synthesis, characterization, and application in reversible CO2 capture. J Mater Chem A 1(23):6810–6821

    Article  Google Scholar 

  39. Xiao M, Zhu J, Ge J, Liu C, Xing W (2015) The enhanced electrocatalytic activity and stability of supported Pt nanoparticles for methanol electro-oxidation through the optimized oxidation degree of carbon nanotubes. J Power Sources 281:34–43

    Article  Google Scholar 

  40. Carvalho RC, Mandil A, Prathish KP, Amine A, Brett CMA (2013) Carbon nanotube, carbon black and copper nanoparticle modified screen printed electrodes for amino acid determination. Electroanal 25(4):903–913

    Article  Google Scholar 

  41. Mikolajczuk-Zychora A, Borodzinski A, Kedzierzawski P, Mierzwa B, Mazurkiewicz-Pawlicka M, Stobinski L, Ciecierska E, Zimoch A, Opałło M (2016) Highly active carbon supported Pd cathode catalysts for direct formic acid fuel cells. Appl Surf Sci 388:645–652

    Article  Google Scholar 

  42. Duan X, O’Donnell K, Sun H, Wang Y, Wang S (2015) Sulfur and nitrogen Co-doped graphene for metal-free catalytic oxidation reactions. Small 11(25):3036–3044

    Article  Google Scholar 

  43. Zhou Y, Neyerlin K, Olson TS, Pylypenko S, Bult J, Dinh HN, Gennett T, Shao Z, O’Hayre R (2010) Enhancement of Pt and Pt-alloy fuel cell catalyst activity and durability via nitrogen-modified carbon supports. Energy & Environ Sci 3(10):1437–1446

    Article  Google Scholar 

  44. Wu G, Swaidan R, Li D, Li N (2008) Enhanced methanol electro-oxidation activity of PtRu catalysts supported on heteroatom-doped carbon. Electrochim Acta 53(26):7622–7629

    Article  Google Scholar 

  45. Perazzolo V, Durante C, Pilot R, Paduano A, Zheng J, Rizzi GA, Martucci A, Granozzi G, Gennaro A (2015) Nitrogen and sulfur doped mesoporous carbon as metal-free electrocatalysts for the in situ production of hydrogen peroxide. Carbon 95:949–963

    Article  Google Scholar 

  46. Shen W, Fan W (2013) Nitrogen-containing porous carbons: synthesis and application. J Mater Chem A 1(4):999–1013

    Article  Google Scholar 

  47. Wu G, Li D, Dai C, Wang D, Li N (2008) Well-dispersed high-loading Pt nanoparticles supported by shell–core nanostructured carbon for methanol electrooxidation. Langmuir 24:3566–3575

    Article  Google Scholar 

  48. Xu T-T, Zhang J, Song J-M, Niu H-L, Mao C-J, Zhang S-Y, Shen Y-H (2016) Synthesis of ZnO-loaded Co0.85Se nanocomposites and their enhanced performance for decomposition of hydrazine hydrate and catalytic hydrogenation of p-nitrophenol. Appl Catal A 515:83–90

    Article  Google Scholar 

  49. Feng J, Wang Q, Fan D, Ma L, Jiang D, Xie J, Zhu J (2016) Nickel-based xerogel catalysts: synthesis via fast sol–gel method and application in catalytic hydrogenation of p-nitrophenol to p-aminophenol. Appl Surf Sci 382:135–143

    Article  Google Scholar 

  50. Yang Y, Sun C, Li X, Yang F, Zhang W, Zhang X, Ren Y (2015) New route toward integrating large nickel nanocrystals onto mesoporous carbons. Appl Catal B 165:94–102

    Article  Google Scholar 

  51. Liu Q, Jin J, Zhang J (2013) NiCo2S4@graphene as a bifunctional electrocatalyst for oxygen reduction and evolution reactions. ACS Appl Mater Interfaces 5:5002–5008

    Article  Google Scholar 

  52. Lin J-Y, Chou S-W (2013) Highly transparent NiCo2S4 thinfilm as an effective catalyst toward triiodide reduction in dye-sensitized solar cells. Electrochem Commun 37:11–14

    Article  Google Scholar 

  53. Wen P, Fan M, Yang D, Wang Y, Cheng H, Wang J (2016) An asymmetric supercapacitor with ultrahigh energy density based on nickle cobalt sulfide nanocluster anchoring multi-wall carbon nanotubes hybrid. J Power Sources 320:28–36

    Article  Google Scholar 

  54. Guo P, Xiao F, Liu Q, Liu H, Guo Y, Gong JR, Wang S, Liu Y (2013) One-pot microbial method to synthesize dual-doped graphene and its use as high-performance electrocatalyst. Sci Rep 3:3499

    Article  Google Scholar 

  55. Li D, Gong Y, Pan C (2016) Facile synthesis of hybrid CNTs/NiCo2S4 composite for high performance supercapacitors. Sci Rep 6:29788

    Article  Google Scholar 

  56. Estrade-Szwarckopf H (2004) XPS photoemission in carbonaceous materials: a “defect” peak beside the graphitic asymmetric peak. Carbon 42(8):1713–1721

    Article  Google Scholar 

  57. Zhang X, Zhu J, Tiwary CS, Ma Z, Huang H, Zhang J, Lu Z, Huang W, Wu Y (2016) Palladium nanoparticles supported on nitrogen and sulfur dual-doped graphene as highly active electrocatalysts for formic acid and methanol oxidation. ACS Appl Mater Interfaces 8:10858–10865

    Article  Google Scholar 

  58. Wang H, Maiyalagan T, Wang X (2012) Review on recent progress in nitrogen-doped graphene: synthesis, characterization, and its potential applications. ACS Catal 2(5):781–794

    Article  Google Scholar 

  59. Huo J, Wu J, Zheng M, Tu Y, Lan Z (2016) Flower-like nickel cobalt sulfide microspheres modified with nickel sulfide as Pt-free counter electrode for dye-sensitized solar cells. J Power Sources 304:266–272

    Article  Google Scholar 

  60. Maksod I, Hegazy E, Kenawy S, Saleh T (2009) Synthesis and characterization of nano-sized nickel catalyst supported on SiO2–Al2O3. Appl Surf Sci 255:3471–3479

    Article  Google Scholar 

  61. Sun J, Fu Y, He G, Sun X, Wang X (2014) Catalytic hydrogenation of nitrophenols and nitrotoluenes over a palladium/graphene nanocomposite. Catal Sci Technol 4(6):1742–1748

    Article  Google Scholar 

  62. Liu Q-S, Zheng T, Wang P, Jiang J-P, Li N (2010) Adsorption isotherm, kinetic and mechanism studies of some substituted phenols on activated carbon fibers. Chem Eng J 157(2):348–356

    Article  Google Scholar 

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Acknowledgements

This work was supported by NSF of China (Nos. 51572125, 51472101), the Fundamental Research Funds for the Central Universities (No. 30916014103), the Opening Project of the Jiangsu Key Laboratory for Chemistry of Low-Dimensional Materials and PAPD of Jiangsu.

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Authors and Affiliations

  1. Key Laboratory of Soft Chemistry and Functional Materials, Nanjing University of Science and Technology, Nanjing, 210094, China

    Jiawei Xia, Yongsheng Fu & Xin Wang

  2. Key Laboratory of Fine Petrochemical Engineering, Changzhou University, Changzhou, 213164, China

    Jiawei Xia, Guangyu He & Xiaoqiang Sun

  3. Jiangsu Key Laboratory for Chemistry of Low-Dimensional Materials, Huaiyin Normal University, Huai’an, 223300, China

    Lili Zhang

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  1. Jiawei Xia
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  2. Lili Zhang
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  3. Yongsheng Fu
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  4. Guangyu He
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  6. Xin Wang
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Correspondence to Xin Wang.

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10853_2017_1852_MOESM1_ESM.docx

SEM images of the pristine NiCo2S4 and NiCo2S4-x/NCB catalysts (x=10, 20, 30, 40, 50 and 60); Nitrogen adsorption–desorption isotherms and BJH pore size distribution of the CB and NCB supports; c/c 0 versus time and pseudo-first-order plot of ln(c/c 0) against reaction time for the hydrogenation of p-NP catalyzed by nickel sulfide, cobalt sulfide and NiCo2S4; UV-vis spectra of p-NP reduced to p-AP catalyzed by the pristine NiCo2S4 and NiCo2S4-x/NCB catalysts (x=10, 20, 30, 40, 50 and 60); UV-vis spectra of o-NP reduced to o-AP and m-NP reduced to m-AP catalyzed by NiCo2S4-30/NCB; c/c 0 versus time and pseudo-first-order plot of ln(c/c 0) against reaction time for the hydrogenation of p-NP catalyzed by CB, NCB, NiCo2S4-30/CB and NiCo2S4-30/NCB; UV-vis spectra of p-NP reduced to p-AP catalyzed by NiCo2S4 and NiCo2S4-30/NCB under different temperatures; Global XPS spectra of carbon black and N-doped carbon black; C 1s and N 1s core-level XPS spectra of N-doped carbon black; Leaching test of the NiCo2S4-30/NCB catalyst. (DOCX 2593 kb)

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Xia, J., Zhang, L., Fu, Y. et al. Nitrogen-doped carbon black supported NiCo2S4 catalyst for hydrogenation of nitrophenols under mild conditions. J Mater Sci 53, 4467–4481 (2018). https://doi.org/10.1007/s10853-017-1852-5

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