Yifen HU, Pengyu GAO, Yingying GU, Chuan ZHANG, Lizhen HUANG, Yunting HU, Yarui AN, Zhen XU

Size-controllable carbon spheres doped Ni (II) for enhancing the catalytic oxidation of methanol

Ni(II)/CSs were prepared using a simple two-step hydrothermal method. The morphology and composition of the catalysts were studied with scanning electron microscope, transmission electron microscope, and X-ray diffraction. Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy showed that the surface of the prepared carbon spheres was rich in hydroxyl groups, which was beneficial to remove CO intermediates, and therefore, improving the catalytic efficiency and the antipoisoning ability of the catalysts. The results of cyclic voltammetry and chronoamperometry showed that the electrocatalytic activity and stability of Ni(II)/CSs were higher than that of unloaded NiAc under alkaline environment. When the nickel content was 5 wt.%, the peak oxidation current density of methanol on Ni(II)/CSs electrocatalyst reached the maximum of 34.54 mA/cm2 , which was about 1.8 times that of unloaded NiAc. These results indicate that Ni(II)/CSs has potential applications in the electrocatalytic oxidation of methanol.

PDF

___

1. Montoya JH, Seitz LC, Chakthranont P, Vojvodic A, Jaramillo TF et al. Materials for solar fuels and chemicals. Nature Materials 2017; 16 (1): 70-81. doi: 10.1038/nmat4778
2. Cheng F, Chen J. Metal-air batteries: from oxygen reduction electrochemistry to cathode catalysts. Chemical Society Reviews 2012; 41 (6): 2172-2192. doi: 10.1039/c1cs15228a
3. Lyu F, Yu S, Li M, Wang Z, Nan B et al. Supramolecular hydrogel directed self-assembly of C- and N-doped hollow CuO as highperformance anode materials for Li-ion batteries. Chemical Communications 2017; 53 (13): 2138-2141. doi: 10.1039/c6cc09702b
4. Feng Y, Liu H, Yang J. A selective electrocatalyst-based direct methanol fuel cell operated at high concentrations of methanol. Science Advances 2017; 3 (6): e1700580. doi: 10.1126/sciadv.1700580
5. Wang Z-L, Xu D, Xu J-J, Zhang X-B. Oxygen electrocatalysts in metal-air batteries: from aqueous to nonaqueous electrolytes. Chemical Society Reviews 2014; 43 (22): 7746-7786. doi: 10.1039/c3cs60248f
6. Li G, Pickup PG. Analysis of performance losses of direct ethanol fuel cells with the aid of a reference electrode. Journal of Power Sources 2006; 161 (1): 256-263. doi: 10.1016/j.jpowsour.2006.03.071
7. Hasan M, Newcomb SB, Rohan JF, Razeeb KM. Ni nanowire supported 3D flower-like Pd nanostructures as an efficient electrocatalyst for electrooxidation of ethanol in alkaline media. Journal of Power Sources 2012; 218: 148-156. doi: 10.1016/j.jpowsour.2012.06.017
8. Zhu LD, Zhao TS, Xu JB, Liang ZX. Preparation and characterization of carbon-supported sub-monolayer palladium decorated gold nanoparticles for the electro-oxidation of ethanol in alkaline media. Journal of Power Sources 2009; 187 (1): 80-84. doi: 10.1016/j. jpowsour.2008.10.089
9. Rossmeisl J, Ferrin P, Tritsaris GA, Nilekar AU, Koh S et al. Bifunctional anode catalysts for direct methanol fuel cells. Energy & Environmental Science 2012; 5 (8): 8335-8342. doi: 10.1039/c2ee21455e
10. Yang Y, Luo L-M, Zhang R-H, Du J-J, Shen P-C et al. Free-standing ternary PtPdRu nanocatalysts with enhanced activity and durability for methanol electrooxidation. Electrochimica Acta 2016; 222: 1094-1102. doi: 10.1016/j.electacta.2016.11.080
11. Zhan G, Fu Z, Sun D, Pan Z, Xiao Z et al. Platinum nanoparticles decorated robust binary transition metal nitride-carbon nanotubes hybrid as an efficient electrocatalyst for the methanol oxidation reaction. Journal of Power Sources 2016; 326: 84-92. doi: 10.1016/j. jpowsour.2016.06.112
12. Sevilla M, Fuertes AB. The production of carbon materials by hydrothermal carbonization of cellulose. Carbon 2009; 47 (9): 2281-2289. doi: 10.1016/j.carbon.2009.04.026
13. Yu M, Chen J, Liu J, Li S, Ma Y et al. Mesoporous $NiCo_2O_4$ nanoneedles grown on 3D graphene-nickel foam for supercapacitor and methanol electro-oxidation. Electrochimica Acta 2015; 151: 99-108. doi: 10.1016/j.electacta.2014.10.156
14. Dong B, Li W, Huang XX, Ali Z, Zhang T et al. Fabrication of hierarchical hollow Mn doped Ni(OH)2 nanostructures with enhanced catalytic activity towards electrochemical oxidation of methanol. Nano Energy 2019; 55: 37-41. doi: 10.1016/j.nanoen.2018.10.050
15. Ghouri ZK, Barakat NAM, Obaid M, Lee JH, Kim HY. $Co/CeO_2$ -decorated carbon nanofibers as effective non-precious electro-catalyst for fuel cells application in alkaline medium. Ceram International 2015; 41 (2): 2271-2278. doi: 10.1016/j.ceramint.2014.10.031
16. Jothi PR, Kannan S, Velayutham G. Enhanced methanol electro-oxidation over in-situ carbon and graphene supported one dimensional$NiMoO_4$ nanorods. Journal of Power Sources 2015; 277: 350-359. doi: 10.1016/j.jpowsour.2014.11.137
17. Song M-C, Zhang R-H, Zhang X-F, Zhao C-Y, Cui X-M et al. Effect of chromium addition on microstructures and electrochemicalproperties of $V_2.1TiNiO_3$ alloy. Chinese Journal of Inorganic Chemistry 2016; 32 (6): 975-982. doi: 10.11862/cjic.2016.124
18. Wu N, Liu X, Zhao C, Cui C, Xia A. Effects of particle size on the magnetic and microwave absorption properties of carbon-coated nickel nanocapsules. Journal of Alloys and Compounds 2016; 656: 628-634. doi: 10.1016/j.jallcom.2015.10.027
19. Sneed BT, Young AP, Jalalpoor D, Golden MC, Mao SJ et al. Shaped Pd-Ni-Pt core-sandwich-shell nanoparticles: influence of ni sandwich layers on catalytic electrooxidations. Acs Nano 2014; 8 (7): 7239-7250. doi: 10.1021/nn502259g
20. Rahim MAA, Hameed RMA, Khalil MW. Nickel as a catalyst for the electro-oxidation of methanol in alkaline medium. Journal of Power Sources 2004; 134 (2): 160-169. doi: 10.1016/j.jpowsour.2004.02.034
21. Barakat NAM, Yassin MA, Al-Mubaddel FS, Amen MT. New electrooxidation characteristic for Ni-based electrodes for wide application in methanol fuel cells. Applied Catalysis A, General 2018; 555: 148-154. doi: 10.1016/j.apcata.2018.02.016
22. Cheng Y, Xu C, Shen PK, Jiang SP. Effect of nitrogen-containing functionalization on the electrocatalytic activity of PtRu nanoparticles supported on carbon nanotubes for direct methanol fuel cells. Applied Catalysis B-Environmental 2014; 158: 140-149. doi: 10.1016/j. apcatb.2014.04.017
23. Nassr AAA, Sinev I, Pohl MM, Grunert W, Bron M. Rapid Microwave-Assisted Polyol Reduction for the Preparation of Highly Active PtNi/CNT Electrocatalysts for Methanol Oxidation. ACS Catalysis 2014; 4 (8): 2449-2462. doi: 10.1021/cs401140g
24. Barakat NAM, El-Newehy M, Al-Deyab SS, Kim HY. Cobalt/copper-decorated carbon nanofibers as novel non-precious electrocatalyst for methanol electrooxidation. Nanoscale Research Letters 2014; 9: 2. doi: 10.1186/1556-276x-9-2
25. Hu GZ, Nitze F, Barzegar HR, Sharifi T, Mikolajczuk A et al. Palladium nanocrystals supported on helical carbon nanofibers for highly efficient electro-oxidation of formic acid, methanol and ethanol in alkaline electrolytes. Journal of Power Sources 2012; 209: 236-242. doi: 10.1016/j.jpowsour.2012.02.080
26. Zhang YM, Liu Y, Liu WH, Li XY, Mao LQ. Synthesis of honeycomb-like mesoporous nitrogen-doped carbon nanospheres as Pt catalyst supports for methanol oxidation in alkaline media. Applied Surface Science 2017; 407: 64-71. doi: 10.1016/j.apsusc.2017.02.158
27. Zhai CP, Li SS, Wang JH, Liu Y. Nitrogen-doped porous carbon sphere supported Pt nanoparticles for methanol and ethanol electrooxidation in alkaline media. RSC Advances 2018; 8 (63): 36353-36359. doi: 10.1039/c8ra07848c
28. Li K, Jin Z, Ge JJ, Liu CP, Xing W. Platinum nanoparticles partially-embedded into carbon sphere surfaces: a low metal-loading anode catalyst with superior performance for direct methanol fuel cells. Journal of Materials Chemistry A 2017; 5 (37): 19857-19865. doi: 10.1039/c7ta06700c
29. Wang Q, Li H, Chen LQ, Huang XJ. Monodispersed hard carbon spherules with uniform nanopores. Carbon 2001; 39 (14): 2211-2214. doi: 10.1016/s0008-6223(01)00040-9
30. Hu B, Wang K, Wu L, Yu S-H, Antonietti M et al. Engineering Carbon Materials from the Hydrothermal Carbonization Process of Biomass. Advanced Materials 2010; 22 (7): 813-828. doi: 10.1002/adma.200902812
31. Titirici M-M, Antonietti M. Chemistry and materials options of sustainable carbon materials made by hydrothermal carbonization. Chemical Society Reviews 2010; 39 (1): 103-116. doi: 10.1039/b819318p
32. Sevilla M, Fuertes AB. Chemical and Structural Properties of Carbonaceous Products Obtained by Hydrothermal Carbonization of Saccharides. Chemistry-A European Journal 2009; 15 (16): 4195-4203. doi: 10.1002/chem.200802097
33. Ryu J, Suh Y-W, Suh DJ, Ahn DJ. Hydrothermal preparation of carbon microspheres from mono-saccharides and phenolic compounds. Carbon 2010; 48 (7): 1990-1998. doi: 10.1016/j.carbon.2010.02.006.
34. Li M, Li W, Liu S. Hydrothermal synthesis, characterization, and KOH activation of carbon spheres from glucose. Carbohydrate Research 2011; 346 (8): 999-1004. doi: 10.1016/j.carres.2011.03.020
35. Kang S, Li X, Fan J, Chang J. Characterization of Hydrochars Produced by Hydrothermal Carbonization of Lignin, Cellulose, D-Xylose, and Wood Meal. Industrial & Engineering Chemistry Research 2012; 51 (26): 9023-9031. doi: 10.1021/ie300565d
36. You B, Wang L, Yao L, Yang J. Three dimensional N-doped graphene-CNT networks for supercapacitor. Chemical Communications 2013; 49 (44): 5016-5018. doi: 10.1039/c3cc41949e
37. Wei L, Sevilla M, Fuertes AB, Mokaya R, Yushin G. Hydrothermal Carbonization of Abundant Renewable Natural Organic Chemicals for High-Performance Supercapacitor Electrodes. Advanced Energy Materials 2011; 1 (3): 356-361. doi: 10.1002/aenm.201100019
38. Yu H, Gu L, Wu S, Dong G, Qiao X et al. Hydrothermal carbon nanospheres assisted-fabrication of PVDF ultrafiltration membranes with improved hydrophilicity and antifouling performance. Separation and Purification Technology 2020; 247: 116889. doi: 10.1016/j. seppur.2020.116889
39. Gu YY, Gao PY, Yu ZZ, Hu YF, Xu Z et al. Honeycomb-like Mesoporous $NiO-SnO_2 /SO_4^{2}- Solid Superacid for the Efficient Reaction of Methanol Oxidation. International Journal of Electrochemical Science 2020; 15 (3): 2481-2498. doi: 10.20964/2020.03.41
40. Yu X, Zhang K, Tian N, Qin A, Liao L et al. Biomass carbon derived from sisal fiber as anode material for lithium-ion batteries. Materials Letters 2015; 142: 193-196. doi: 10.1016/j.matlet.2014.11.160
41. Yu J, Ni Y, Zhai M. Simple solution-combustion synthesis of Ni-NiO@C nanocomposites with highly electrocatalytic activity for methanol oxidation. Journal of Physics and Chemistry of Solids 2018; 112: 119-126. doi: 10.1016/j.jpcs.2017.09.022
42. Sun H, Xu G-L, Xu Y-F, Sun S-G, Zhang X-F et al. A composite material of uniformly dispersed sulfur on reduced graphene oxide: Aqueous one-pot synthesis, characterization and excellent performance as the cathode in rechargeable lithium-sulfur batteries. Nano Research 2012; 5 (10): 726-738. doi: 10.1007/s12274-012-0257-7
43. Wu L, Zhou Y, Nie W, Song L, Chen P. Synthesis of highly monodispersed teardrop-shaped core-shell $SiO_2/TiO_2$ nanoparticles and their photocatalytic activities. Applied Surface Science 2015; 351: 320-326. doi: 10.1016/j.apsusc.2015.05.152
44. Qian W, Gao Q, Zhang H, Tian W, Li Z et al. Crosslinked Polypyrrole Grafted Reduced Graphene Oxide-Sulfur Nanocomposite Cathode for High Performance Li-S Battery. Electrochimica Acta 2017; 235: 32-41. doi: 10.1016/j.electacta.2017.03.063
45. Ulas B, Caglar A, Sahin O, Kivrak H. Composition dependent activity of PdAgNi alloy catalysts for formic acid electrooxidation. Journal of Colloid and Interface Science 2018; 532: 47-57. doi: 10.1016/j.jcis.2018.07.120
46. Zhang C, Qian LH, Zhang K, Yuan SL, Xiao JW et al. Hierarchical porous Ni/NiO core-shells with superior conductivity for electrochemical pseudo-capacitors and glucose sensors. Journal of Materials Chemistry A 2015; 3 (19): 10519-10525. doi: 10.1039/c5ta01071c
47. Hameed RMA. Microwave irradiated Ni-MnOx/C as an electrocatalyst for methanol oxidation in KOH solution for fuel cell application. Applied Surface Science 2015; 357: 417-428. doi: 10.1016/j.apsusc.2015.08.201
48. Gu Y, Luo J, Liu Y, Yang H, Ouyang R et al. Synthesis of Bimetallic Ni-Cr Nano-Oxides as Catalysts for Methanol Oxidation in NaOH Solution. Journal of Nanoscience and Nanotechnology 2015; 15 (5): 3743-3749. doi: 10.1166/jnn.2015.9528
49. Chen ST, Wu HB, Tao J, Xin HL, Zhu YM et al. Pt-Ni seed-core-frame hierarchical nanostructures and their conversion to nanoframes for enhanced methanol electro-oxidation. Catalysts 2019; 9 (1): 15. doi: 10.3390/catal9010039
50. Liu X-J, Sun Y-D, Yin X, Jia C, Ma M et al. Enhanced methanol electrooxidation over defect-rich Pt-M (M = Fe, Co, Ni) ultrathin nanowires. Energy & Fuels 2020; 34 (8): 10078-10086. doi: 10.1021/acs.energyfuels.0c01850
51. Yin SL, Wang ZQ, Li CJ, Yu HJ, Deng K et al. Mesoporous Pt@PtM (M = Co, Ni) cage-bell nanostructures toward methanol electrooxidation. Nanoscale Advances 2020; 2 (3): 1084-1089. doi: 10.1039/d0na00020e
52. Yaqoob L, Noor T, Iqbal N, Nasir H, Zaman N. Development of Nickel-BTC-MOF-Derived nanocomposites with rGO towards electrocatalytic oxidation of methanol and its product analysis. Catalysts 2019; 9 (10): 21. doi: 10.3390/catal9100856
53. Wang TJ, Huang H, Wu XR, Yao HC, Li FM et al. Self-template synthesis of defect-rich NiO nanotubes as efficient electrocatalysts for methanol oxidation reaction. Nanoscale 2019; 11 (42): 19783-19790. doi: 10.1039/c9nr06304h
54. Wang BR, Cao Y, Chen Y, Wang RZ, Wang XH et al. Microwave-assisted fast synthesis of hierarchical $NiCo_2O_4$ nanoflower-like supportedNi$(OH)_2$ nanoparticles with an enhanced electrocatalytic activity towards methanol oxidation. Inorganic Chemistry Frontiers 2018; 5 (1):172-182. doi: 10.1039/c7qi00583k