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1 Supporting Information Ultrafine Pt Nanoparticles and Amorphous Nickel Supported on 3D Mesoporous Carbon Derived from Cu-MOF for Efficient Methanol Oxidation and Nitrophenol Reduction Xue-Qian Wu, 1,2 Jun Zhao, 1 Ya-Pan Wu, 1 Wen-Wen Dong, 1 Dong-Sheng Li,* 1 Jian-Rong Li, 2 Qichun Zhang * 3 1. College of Material and Chemical Engineering, Hubei Provincial Collaborative Innovation Center for New Energy Microgrid, Key Laboratory of Inorganic Nonmetallic Crystalline and Energy Conversion Materials, China Three Gorges University, Yichang , China. 2. Beijing Key Laboratory for Green Catalysis and Separation and Department of Chemistry and Chemical Engineering, College of Environmental and Energy Engineering, Beijing University of Technology, Beijing , P. R. China. 3. School of Materials Science and Engineering, Nanyang Technological University, Singapore, , Singapore. These authors contributed equally to the work. * To whom correspondence should be addressed. lidongsheng1@126.com qczhang@ntu.edu.sg. S-1
2 Figure S1. The XRD patterns of HKUST-1 sample. Figure S2. The typical SEM image of HKUST-1 sample. S-2
3 Figure S3. The SEM images of NPC-800/900/1000 sample. Figure S4. The XRD patterns of C550 sample (denotes the sample of HKUST-1 carbonized at 550oC without etching treatment as C550 ). XRD patterns of C550 display three diffraction peaks at around 2θ = 43.2o, 50.4o and 74.1o, which can be assigned to the (111), (200) and (220) planes of a crystalline cubic Cu. S-3
4 Figure S5. SEM micrograph and EDS spectrum of the as-fabricated Pt/NPC-800/900/1000. Figure S6. HRTEM images of the obtained Pt/NPC-900( Pt nanoparticles uniformly distributed on the surface or embedded within the carbon matrix with an average particle size of 2-3 nm). S-4
5 Figure S7. The XRD patterns of as-prepared Ni/NPC-900 (without diffraction peaks of any nickel species ). Figure S8. SEM micrograph and EDS spectrum of the as fabricated Ni/NPC S-5
6 Figure S9. HRTEM images of as prepared Ni/NPC-900 (the cellular-like NPC-900 was covered with amorphous nickel ). Figure S10. Cyclic test of Pt/NPC-900 under the same experimental condition. S-6
7 Figure S11. Cyclic test of Ni/NPC-900 under the same experimental condition. Figure S12. The geometry of 2/3/4-NP molecules. S-7
8 Table S1 Comparison of activity between catalysts in this study and previously reported MOR catalysts Name of Catalyst Mass activity (ma mg -1 ) Scanning rate (mv S -1 ) Experimental conditions References Pt-Cu octahedron alloy ~ M CH 3 OH+0.5 M H 2 SO 4 CrystEngComm. 2016, 18, Pt/Ni alloy M CH 3 OH M HClO 4 Nano Lett. 2016, 16, ChemCatChem. 2016, 8, Pt-Ni/BNG M CH 3 OH+0.5 M H 2 SO PtNPs/R-3DNG M H 2 SO M CH 3 OH Chem. Commun. 2016, 52, PtPdCu alloy M H 2 SO 4 +1 M CH 3 OH ACS Appl. Mater. Interfaces 2015, 7, Pt nanorod M HClO M CH 3 OH Angew. Chem. Int. Ed. 2013, 52, Pt 3 Ti nanoparticle M HClO M CH 3 OH J. Am. Chem. Soc. 2014, 136, PtPd nanocage M H 2 SO 4 +1 M CH 3 OH J. Am. Chem. Soc. 2013, 135, AuAg network ~ M KOH+2 M CH 3 OH Nat. Commun. 2018, 9, 521. Pt/SnO 2 ~ M H 2 SO M CH 3 OH ACS Appl. Mater. Interface 2017, 9, Pt/PANI ~ M HClO 4 +1 M CH 3 OH ACS Appl. Mater. Interface 2017, 9, Au@Pt 5004 (Based M KOH+0.5 M CH 3 OH ACS Appl. Mater. Interface 2017, S-8
9 on Pt) 9, Pt/CPE ~ M H 2 SO 4 +1 M CH 3 OH Electrochimica Acta 2017, 242, Pt/NPC M H 2 SO 4 +1 M CH 3 OH This work Pt/NPC M H 2 SO 4 +1 M CH 3 OH This work Pt/NPC M H 2 SO 4 +1 M CH 3 OH This work S-9
10 Table S2 Comparison of activity between catalysts in this study and previously reported Ni-based MOR catalysts Name of Catalyst Mass activity (ma mg -1 ) Scanning rate (mv S -1 ) Experimental conditions References CNFs-Ni M KOH M CH 3 OH RSC Adv. 2017, 7, NiO M KOH M CH 3 OH Electrochimica. Acta 2011, 56, Ni@CNTs M KOH + 1 M CH 3 OH J. Mater. Chem. A 2017, 5, Ni-P@RGO M KOH M CH 3 OH Electrochem. Commun. 2013, 35, Ni-P M KOH M CH 3 OH Electrochem. Commun. 2013, 35, H-NiCo 2 O 4 ~ M NaOH M CH 3 OH RSC Adv. 2016, 6, Ni/graphite M KOH M CH 3 OH J. Power Sour. 2004, 134, Ni DES M KOH M CH 3 OH Int. J. Hydrogen Energy 2014, 39, Ni/rGO M KOH + 1 M CH 3 OH Chem. Commun. 2018, 54, Ni/NPC M NaOH + 1 M CH 3 OH This work S-10
11 Table S3 Summary of rate constants of other similar 4-nitrophenol reduction reactions catalyzed by previously reported catalysts Name of Catalyst Apparent reaction rate constants ( 10-3 s -1 ) Reference Ag@AuNPs 0.69 Sci. Bull 2016, 61, Ag/AuNPs 0.87 Sci. Bull 2016, 61, Colloidal Pt-NPs 3.2 J. Ind. Eng. Chem. 2015, 22, Au-Ag bimetallic nanoparticles 1.1 Spectrochim. Acta., 2015, 137, Cu 2 O@RGO 14.3 RSC Adv. 2015, 5, CuFe 2 O Int. J. Hydrogen Ener. 2014, 39, AuNPs@CPF 5.05 Chem. Eur. J. 2016, 22, Pd@Y-DDQ 5.0 Sci. Rep. 2016, 6, Au/ZSBA-PL Nano Res. 2016, 9, Au core/porous shell nanoparticles 3.65 Nanoscale 2016, 8, Pt/NPC This work Ni/NPC This work S-11
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