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 443002, 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 100124, P. R. China. 3. School of Materials Science and Engineering, Nanyang Technological University, Singapore, 639798, Singapore. These authors contributed equally to the work. * To whom correspondence should be addressed. Email: lidongsheng1@126.com Email: qczhang@ntu.edu.sg. S-1
Figure S1. The XRD patterns of HKUST-1 sample. Figure S2. The typical SEM image of HKUST-1 sample. S-2
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
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
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-900.. S-5
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
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
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 ~140 50 1M CH 3 OH+0.5 M H 2 SO 4 CrystEngComm. 2016, 18, 3216-3222. Pt/Ni alloy 800 50 0.2 M CH 3 OH + 0.1 M HClO 4 Nano Lett. 2016, 16, 2762-2767. ChemCatChem. 2016, 8, Pt-Ni/BNG 350 50 0.5 M CH 3 OH+0.5 M H 2 SO 4 1410-1416. PtNPs/R-3DNG 1600 50 1.0 M H 2 SO 4 +0.5 M CH 3 OH Chem. Commun. 2016, 52, 382-385. PtPdCu alloy 1505 50 0.5 M H 2 SO 4 +1 M CH 3 OH ACS Appl. Mater. Interfaces 2015, 7, 26333-26339. Pt nanorod 209 50 0.1 M HClO 4 +0.5 M CH 3 OH Angew. Chem. Int. Ed. 2013, 52, 8050-8053. Pt 3 Ti nanoparticle 475 50 0.1 M HClO 4 + 1 M CH 3 OH J. Am. Chem. Soc. 2014, 136, 10206-10209. PtPd nanocage 580 50 0.5 M H 2 SO 4 +1 M CH 3 OH J. Am. Chem. Soc. 2013, 135, 16762-16765. AuAg network ~15 10 0.5 M KOH+2 M CH 3 OH Nat. Commun. 2018, 9, 521. Pt/SnO 2 ~1600 50 0.5 M H 2 SO 4 +0.5 M CH 3 OH ACS Appl. Mater. Interface 2017, 9, 26921-26927. Pt/PANI ~870 50 0.1 M HClO 4 +1 M CH 3 OH ACS Appl. Mater. Interface 2017, 9, 30278 30282. Au@Pt 5004 (Based 50 0.1 M KOH+0.5 M CH 3 OH ACS Appl. Mater. Interface 2017, S-8
on Pt) 9, 32688 32697. Pt/CPE ~130 50 0.5 M H 2 SO 4 +1 M CH 3 OH Electrochimica Acta 2017, 242, 165-172. Pt/NPC-800 790 50 0.5 M H 2 SO 4 +1 M CH 3 OH This work Pt/NPC-900 1195 50 0.5 M H 2 SO 4 +1 M CH 3 OH This work Pt/NPC-1000 980 50 0.5 M H 2 SO 4 +1 M CH 3 OH This work S-9
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 400 50 1 M KOH + 0.5 M CH 3 OH RSC Adv. 2017, 7, 14152-14158. NiO 84 20 0.005 M KOH + 0.1 M CH 3 OH Electrochimica. Acta 2011, 56, 5656-5666. Ni@CNTs 966 50 1 M KOH + 1 M CH 3 OH J. Mater. Chem. A 2017, 5, 9946-9951. Ni-P@RGO 117 10 1 M KOH + 0.5 M CH 3 OH Electrochem. Commun. 2013, 35, 108-111. Ni-P 60 10 1 M KOH + 0.5 M CH 3 OH Electrochem. Commun. 2013, 35, 108-111. H-NiCo 2 O 4 ~80 50 1 M NaOH + 0.5 M CH 3 OH RSC Adv. 2016, 6, 30488-30497. Ni/graphite 316 50 1 M KOH + 0.5 M CH 3 OH J. Power Sour. 2004, 134, 160-169. Ni DES 3 10 0.005 M KOH + 0.1 M CH 3 OH Int. J. Hydrogen Energy 2014, 39, 10892-10901. Ni/rGO 1600 50 1 M KOH + 1 M CH 3 OH Chem. Commun. 2018, 54, 1563-1566. Ni/NPC-900 449.8 50 1 M NaOH + 1 M CH 3 OH This work S-10
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, 1525-1535. Ag/AuNPs 0.87 Sci. Bull 2016, 61, 1525-1535. Colloidal Pt-NPs 3.2 J. Ind. Eng. Chem. 2015, 22, 185-191. Au-Ag bimetallic nanoparticles 1.1 Spectrochim. Acta., 2015, 137, 185-192. Cu 2 O@RGO 14.3 RSC Adv. 2015, 5, 71259-71267. CuFe 2 O 4 4.05 Int. J. Hydrogen Ener. 2014, 39, 4895-4908. AuNPs@CPF 5.05 Chem. Eur. J. 2016, 22, 2075-2080. Pd@Y-DDQ 5.0 Sci. Rep. 2016, 6, 29728 Au/ZSBA-PL 2.355 Nano Res. 2016, 9, 3099-3115. Au core/porous shell nanoparticles 3.65 Nanoscale 2016, 8, 11707-11717. Pt/NPC-900 11 This work Ni/NPC-900 10 This work S-11