Volume 1, Issue 2, Pages 220-245 (August 2016) Immobilization of Ultrafine Metal Nanoparticles to High-Surface-Area Materials and Their Catalytic Applications  Qi-Long Zhu, Qiang Xu  Chem  Volume 1, Issue 2, Pages 220-245 (August 2016) DOI: 10.1016/j.chempr.2016.07.005 Copyright © 2016 Elsevier Inc. Terms and Conditions

Chem 2016 1, 220-245DOI: (10.1016/j.chempr.2016.07.005) Copyright © 2016 Elsevier Inc. Terms and Conditions

Figure 1 Immobilization of UMNPs to Various High-Surface-Area Materials Chem 2016 1, 220-245DOI: (10.1016/j.chempr.2016.07.005) Copyright © 2016 Elsevier Inc. Terms and Conditions

Figure 2 Schematic Representation of the Synthesis of Pt Nanoparticles inside an MIL-101 Matrix Using the Double-Solvent Method Adapted with permission from Aijaz et al.13 Copyright 2012 American Chemical Society. Chem 2016 1, 220-245DOI: (10.1016/j.chempr.2016.07.005) Copyright © 2016 Elsevier Inc. Terms and Conditions

Figure 3 Schematic Synthesis of Pd NPs Immobilized by POFs with Tunable Size, Location, and Distribution by a Substituent-Controlled Strategy Adapted from Zhong et al.15 with permission from the Royal Society of Chemistry. Chem 2016 1, 220-245DOI: (10.1016/j.chempr.2016.07.005) Copyright © 2016 Elsevier Inc. Terms and Conditions

Figure 4 Preparation and TEM Images of AuNi@MIL-101 (A) Schematic representation of the immobilization of AuNi NPs by the MIL-101 matrix using DSM combined with a liquid-phase CCR strategy. (B–D) TEM images of AuNi@MIL-101 obtained by reduction using NaBH4 solutions of 0.6 M (B), 0.4 M (C), and 0.2 M (D). Adapted with permission from Zhu et al.16 Copyright 2013 American Chemical Society. Chem 2016 1, 220-245DOI: (10.1016/j.chempr.2016.07.005) Copyright © 2016 Elsevier Inc. Terms and Conditions

Figure 5 MOF-Size-Dependent Catalytic Activity The dependence of the catalytic activity on the size of the MOF crystallites and Pd-particle migration for the reduction of benzophenone with Pd@MIL-101 under mild reaction conditions (24 hr, 20 bar H2, 800 rpm, 50°C, 3 mg catalyst, 0.5 g benzophenone dissolved in 0.73 mL of toluene, and 0.15 mol % Pd). Adapted with permission from Hermannsdörfer et al.59 Copyright 2013 John Wiley and Sons Inc. Chem 2016 1, 220-245DOI: (10.1016/j.chempr.2016.07.005) Copyright © 2016 Elsevier Inc. Terms and Conditions

Figure 6 Redox Reaction for Immobilizing Ag NPs in the MOF Reaction of Ni-MOF incorporating redox-active Ni(II) square-planar macrocyclic complex with Ag(I) ions to generate Ag NPs. Adapted with permission from Moon et al.60 Copyright 2005 John Wiley and Sons Inc. Chem 2016 1, 220-245DOI: (10.1016/j.chempr.2016.07.005) Copyright © 2016 Elsevier Inc. Terms and Conditions

Figure 7 Photocatalytic Hydrogen Evolution by Pt@Zr-MOFs (A) Scheme showing the synergistic photocatalytic evolution of hydrogen via photoinjection of electrons from light-harvesting MOFs (1 and 2) into Pt NPs. (B) Diffuse reflectance spectra and a photograph of suspensions of these samples. (C) Relationship between the amount of K2PtCl4 added in the reaction solution and the amount of Pt deposited inside the MOFs. (D) Time-dependent hydrogen-evolution curves of the samples. Adapted with permission from Wang et al.65 Copyright 2012 American Chemical Society. Chem 2016 1, 220-245DOI: (10.1016/j.chempr.2016.07.005) Copyright © 2016 Elsevier Inc. Terms and Conditions

Figure 8 Schematic Representation of the Preparation of Supported Ultrafine Pd NPs via a Methanol-Mediated Weakly Capping Growth Approach Adapted with permission from Zhu et al.49 Copyright 2015 American Chemical Society. Chem 2016 1, 220-245DOI: (10.1016/j.chempr.2016.07.005) Copyright © 2016 Elsevier Inc. Terms and Conditions

Figure 9 Morphological Evolution of Au/N-PGC (A–D) Bright-field TEM (A), high-angle annular dark-field (HAADF) scanning TEM (B), high-resolution TEM (C), and scanning TEM energy-dispersive X-ray spectroscopy (D) mappings of Au/N-PGC: Au, N, C, and O are shown in (D1), (D2), (D3), and (D4), respectively. (E) High-resolution X-ray photoelectron spectroscopy Au 4f spectrum of Au/N-PGC. The bottom spectrum (red) is from an Au thin film. (F) The average diameter and distribution of Au NPs. Adapted with permission from Liu et al.23 Copyright 2016 American Chemical Society. Chem 2016 1, 220-245DOI: (10.1016/j.chempr.2016.07.005) Copyright © 2016 Elsevier Inc. Terms and Conditions

Figure 10 Illustration of the Synthesis of Ordered Mesoporous Pt@OMC Composites Adapted with permission from Wu et al.75 Copyright 2012 American Chemical Society. Chem 2016 1, 220-245DOI: (10.1016/j.chempr.2016.07.005) Copyright © 2016 Elsevier Inc. Terms and Conditions

Figure 11 Preparation and TEM Images of MWCNT/IL/Au Hybrids Illustration of the preparation procedure (A), TEM image (B), and high-resolution TEM image (C) of multiwalled carbon nanotube/ionic liquid/gold (MWCNT/IL/Au) hybrids. Adapted with permission from Wang et al.77 Copyright 2008 Elsevier Inc. Chem 2016 1, 220-245DOI: (10.1016/j.chempr.2016.07.005) Copyright © 2016 Elsevier Inc. Terms and Conditions

Figure 12 TEM Image and Catalytic Activity of the Catalysts (A and B) TEM image (A) and particle-size distribution (B) of the RhMn-in-CNT catalyst. (C) Activities as a function of time of RhMn-in-CNT and RhMn-out-CNT in syngas conversion at 320°C and 30 bar. Adapted by permission from Macmillan Publishers Ltd: Nature Materials (Pan et al.20), copyright 2007. Chem 2016 1, 220-245DOI: (10.1016/j.chempr.2016.07.005) Copyright © 2016 Elsevier Inc. Terms and Conditions

Figure 13 Preparation and TEM Images of AgPd/rGO (A) Schematic illustration of immobilization of AgPd NPs on rGO by the non-noble metal sacrificial approach. (B and C) TEM images (C is a higher magnification of B) of Ag0.1Pd0.9/rGO. Scale bars represent 50 nm (B) and 10 nm (C). Adapted with permission from Chen et al.21 Copyright 2015 American Chemical Society. Chem 2016 1, 220-245DOI: (10.1016/j.chempr.2016.07.005) Copyright © 2016 Elsevier Inc. Terms and Conditions

Figure 14 TEM Images of Au/rGO Scanning electron microscopy (A), TEM (B and C), and high-angle annular dark-field scanning TEM (D) images of as-synthesized Au/rGO hybrids. Adapted with permission from Yin et al.30 Copyright 2012 American Chemical Society. Chem 2016 1, 220-245DOI: (10.1016/j.chempr.2016.07.005) Copyright © 2016 Elsevier Inc. Terms and Conditions

Figure 15 Catalytic Hydrogen Generation from Formic Acid Time-course plots for hydrogen generation from an aqueous solution (1.0 mL) of formic acid (3.0 M) and sodium formate (1.0 M) in the presence of different Au catalysts (60 mg, 2 wt % Au) at 90°C. Adapted from Yadav et al.33 with permission from the Royal Society of Chemistry. Chem 2016 1, 220-245DOI: (10.1016/j.chempr.2016.07.005) Copyright © 2016 Elsevier Inc. Terms and Conditions

Figure 16 Schematic Representation of Assemblage of Highly Dispersed Ag NPs inside the Channels of SBA-15 Adapted with permission from Sun et al.25 Copyright 2006 American Chemical Society. Chem 2016 1, 220-245DOI: (10.1016/j.chempr.2016.07.005) Copyright © 2016 Elsevier Inc. Terms and Conditions