Abstract：Copper nitrate and trimesic acid were used as raw materials to fabricate octahedral HKUST-1 by hydrothermal method. HKUST-1 was calcined in Ar protective atmosphere and Cu/C nanoparticles were derived through carbothermal reduction reaction. The Cu@Pt/C catalyst was obtained by soaking Cu/C in potassium chloroplatinic acid solution by galvanic displacement. The morphology and microstructure of Cu@Pt/C catalyst as well as its electrocatalytic activity towards methanol were further characterized by SEM, XRD, XPS and cyclic voltammetry (CV). The results show that the as-prepared Cu@Pt/C catalyst retains special octahedral structure of HKUST-1 and has a core-shell structure formed by Pt coating on the surface of Cu. The electrochemically active surface areas (ECSA) measured by cyclic voltammetry curves in H2SO4 solution is 74.3 m2/g, about 1.47 times as much as that of commercial Pt/C. The cyclic voltammetry curves in H2SO4+CH3OH solution shows the ratio of positive sweep peak current density to reverse sweep peak current density Jf/Jb is 2.18, which is much higher than that of commercial Pt/C. Thus Cu@Pt/C catalyst has better electrocatalytic activity to methanol oxidation and better CO tolerance.
龙翔宇, 雷霆, 王坤婵, 詹振翔. 以HKUST-1为前驱体的Cu@Pt/C催化剂的结构及对甲醇的催化氧化性能研究[J]. 粉末冶金材料科学与工程, 2019, 24(3): 289-295.
LONG Xiangyu, LEI Ting, WANG Kunchan, ZHAN Zhenxiang. Structure of Cu@Pt/C catalyst derived from HKUST-1 and its catalytic activity for methanol oxidation. Materials Science and Engineering of Powder Metallurgy, 2019, 24(3): 289-295.
[1] IWASITA T.Electrocatalysis of methanol oxidation[J]. Electrochimica Acta, 2002, 47(22): 3663-3674. [2] YANG L, YANG W, CAI Q.Well-Dispersed ptau nanoparticles loaded into anodic titania nanotubes: A high antipoison and stable catalyst system for methanol oxidation in alkaline media[J]. Journal of Physical Chemistry C, 2010, 111(44): 16613-16617. [3] AMMAM M, EASTON E B.Oxygen reduction activity of binary PtMn/C, ternary PtMnX/C (X=Fe, Co, Ni, Cu, Mo and, Sn) and quaternary PtMnCuX/C (X=Fe, Co, Ni, and Sn) and PtMnMoX/C (X=Fe, Co, Ni, Cu and Sn) alloy catalysts[J]. Journal of Power Sources, 2013, 236(236): 311-320. [4] MA X, LUO L, ZHU L, et al.Pt-Fe catalyst nanoparticles supported on single-wall carbon nanotubes: Direct synthesis and electrochemical performance for methanol oxidation[J]. Journal of Power Sources, 2013, 241(6): 274-280. [5] MIN K J, YUAN Z, MCGINN P J.A comparative study of PtCo, PtCr, and PtCoCr catalysts for oxygen electro-reduction reaction[J]. Electrochimica Acta, 2010, 55(19): 5318-5325. [6] WANG M, ZHANG W, WANG J, et al.Mesoporous hollow PtCu nanoparticles for electrocatalytic oxygen reduction reaction[J]. Journal of Materials Chemistry A, 2013, 1(7): 2391-2394. [7] CUI C H, LI H H, YU S H.Large scale restructuring of porous Pt-Ni nanoparticle tubes for methanol oxidation: A highly reactive, stable, and restorable fuel cell catalyst[J]. Chemical Science, 2011, 2(8): 1611-1614. [8] YU Z, CHAO M, ZHU Y, et al.Hollow core supported Pt monolayer catalysts for oxygen reduction[J]. Catalysis Today, 2013, 202(1): 50-54. [9] HUSSAIN N, GOGOI P, AZHAGANAND V K, et al.Correction: Green synthesis of stable Cu(0) nanoparticles onto reduced graphene oxide nanosheets: a reusable catalyst for the synthesis of symmetrical biaryls from arylboronic acids under base-free conditions[J]. Catalysis Science & Technology, 2015, 5(2): 1251-1260. [10] BRANKOVIC S R, WANG J X, ADŽIĆ R R. Metal monolayer deposition by replacement of metal adlayers on electrode surfaces[J]. Surface Science, 2001, 474(1): L173-L179. [11] BRUSSEL M V, KOKKINIDIS G, VANDENDAEL I, et al.High performance gold-supported platinum electrocatalyst for oxygen reduction[J]. Electrochemistry Communications, 2002, 4(10): 808-813. [12] MINTSOULI, GEORGIEVA, ARMYANOV, et al. Pt-Cu electrocatalysts for methanol oxidation prepared by partial galvanic replacement of Cu/carbon powder precursors[J]. Applied Catalysis B Environmental, 2013, 136/137(21): 160-167. [13] EL-KHATIB K M, HAMEED R M A, AMIN R S, et al. Core-shell structured Cu@Pt nanoparticles as effective electro catalyst for ethanol oxidation in alkaline medium[J]. International Journal of Hydrogen Energy, 2017, 42(21): 14680-14696. [14] PODLOVCHENKO B I, KRIVCHENKO V A, MAKSIMOV Y M, et al.Specific features of the formation of Pt(Cu) catalysts by galvanic displacement with carbon nanowalls used as support[J]. Electrochimica Acta, 2012, 76(8): 137-144. [15] POOCHAI C.Highly active dealloyed Cu@Pt core-shell electro catalyst towards 2-propanol electro oxidation in acidic solution[J]. Applied Surface Science, 2017, 396(396): 1793-1801. [16] ROWSELL J L C, YAGHI O M. Metal-organic frameworks: a new class of porous materials[J]. Microporous & Mesoporous Materials, 2004, 73(1): 3-14. [17] SCHLICHTE K, KRATZKE T, KASKEL S.Improved synthesis, thermal stability and catalytic properties of the metal-organic framework compound Cu3(BTC)2[J]. Microporous & Mesoporous Materials, 2004, 73(1): 81-88. [18] KUMAR R S, KUMAR S S, KULANDAINATHAN M A.Efficient electrosynthesis of highly active Cu3(BTC)2-MOF and its catalytic application to chemical reduction[J]. Microporous & Mesoporous Materials, 2013, 168(3): 57-64. [19] ZHANG R, LIN H, BAO S, et al.Surface polarization enhancement: high catalytic performance of Cu/CuOx/C nanocomposites derived from Cu-BTC for CO oxidation[J]. Journal of Materials Chemistry A, 2016, 4(21): 8412-8420. [20] ZHU H, LI X, WANG F.Synthesis and characterization of Cu@Pt/C core-shell structured catalysts for proton exchange membrane fuel cell[J]. Fuel and Energy Abstracts, 2011, 36(15): 9151-9154. [21] AMELOOT R, PANDEY L, VAN d A M, et al. Patterned film growth of metal-organic frameworks based on galvanic displacement[J]. Chemical Communications, 2010, 46(21): 3735-3737. [22] CHENG W H.Reaction and XRD studies on Cu based methanol decomposition catalysts: Role of constituents and development of high-activity multicomponent catalysts[J]. Applied Catalysis A General, 1995, 130(1): 13-30. [23] El-KHATIB K M, HAMEED R M A, AMIN R S, et al. Core-shell structured Cu@Pt nanoparticles as effective electrocatalyst for ethanol oxidation in alkaline medium[J]. International Journal of Hydrogen Energy, 2017, 42(21): 14680-14696. [24] MINTSOULI I, GEORGIEVA J, ARMYANOV S, et al. Pt-Cu electrocatalysts for methanol oxidation prepared by partial galvanic replacement of Cu/carbon powder precursors[J]. Applied Catalysis B: Environmental, 2013, 136/137(Complete): 160-167. [25] Star-like PtCu nanoparticles supported on graphene with superior activity for methanol electro-oxidation[J]. Electrochimica Acta, 2015, 177: S0013468615006489. [26] LIU Z, Hong L.Electrochemical characterization of the electrooxidation of methanol, ethanol and formic acid on Pt/C and PtRu/C electrodes[J]. Journal of Applied Electrochemistry, 2007, 37(4): 505-510. [27] BEDEN B, KADIRGAN F, LAMY C, et al.Oxidation of methanol on a platinum electrode in alkaline medium: Effect of metal ad-atoms on the electrocatalytic activity[J]. Journal of Electroanalytical Chemistry & Interfacial Electrochemistry, 1982, 142(1): 171-190. [28] SHEN J, HU Y, CHEN L, et al.Pt-Co supported on single-walled carbon nanotubes as an anode catalyst for direct methanol fuel cells[J]. Electrochimica Acta, 2008, 53(24): 7276-7280. [29] TRASATTI S, PETRII O A.Real surface area measurements in electrochemistry[J]. Pure & Applied Chemistry, 1991, 63(5): 711-734. [30] ZHANG J, VUKMIROVIC M B, SASAKI K, et al.Mixed-metal pt monolayer electrocatalysts for enhanced oxygen reduction kinetics[J]. Journal of the American Chemical Society, 2005, 127(36): 12480-12481. [31] RUBAN A, HAMMER B, STOLTZE P, et al.Surface electronic structure and reactivity of transition and noble metals 1[J]. Journal of Molecular Catalysis A Chemical, 1997, 115(3): 421-429. [32] KITCHIN J R, NØRSKOV J K, BARTEAU M A, et al. Modification of the surface electronic and chemical properties of Pt(111) by subsurface 3D transition metals[J]. Journal of Chemical Physics, 2004, 120(21): 10240-10246. [33] TSIAKARAS P E.PtM/C (M=Sn, Ru, Pd, W) based anode direct ethanol-PEMFCs: Structural characteristics and cell performance[J]. Journal of Power Sources, 2007, 171(1): 107-112.
2019, Vol. 24 
