Volume 3, Issue 9, Pages 2219-2240 (September 2019) Enhanced Catalyst Durability for Bio-Based Adipic Acid Production by Atomic Layer Deposition  Amy E. Settle, Nicholas S. Cleveland, Carrie A. Farberow, Davis R. Conklin, Xiangchen Huo, Arrelaine A. Dameron, Ryon W. Tracy, Reuben Sarkar, Elizabeth J. Kautz, Arun Devaraj, Karthikeyan K. Ramasamy, Mike J. Watson, Allyson M. York, Ryan M. Richards, Kinga A. Unocic, Gregg T. Beckham, Michael B. Griffin, Katherine E. Hurst, Eric C.D. Tan, Steven T. Christensen, Derek R. Vardon  Joule  Volume 3, Issue 9, Pages 2219-2240 (September 2019) DOI: 10.1016/j.joule.2019.06.022 Copyright © 2019 Elsevier Inc. Terms and Conditions

Joule 2019 3, 2219-2240DOI: (10.1016/j.joule.2019.06.022) Copyright © 2019 Elsevier Inc. Terms and Conditions

Figure 1 Top (Left) and Side (Middle, Right) Views of the Minimum Energy Geometries of Muconic Acid and Adipic Acid Adsorbed at the Undercoordinated Step Edge of the Pd(755) Surface Blue, red, gray, and white spheres represent Pd, O, C, and H, respectively. Joule 2019 3, 2219-2240DOI: (10.1016/j.joule.2019.06.022) Copyright © 2019 Elsevier Inc. Terms and Conditions

Figure 2 Characterization of the 100-mg ALD-Coated 0.5 wt % Pd/TiO2 Catalyst (A) SEM image of catalyst particle. (B) SEM-EDS map showing the uniform distribution of Al on the exterior surface of the catalyst. (C) APT elemental map of the catalyst 3D needle specimen. (D and E) APT Slice 1 (D) and Slice 2 (E) showing sample pores back-filled with Pt. (F–I) APT elemental analysis indicative of the TiO2 support (F), Pt used to back-fill pores (G), Pd particles (H), and Al2O3 deposited by ALD (I). (J) DF-STEM image showing highly dispersed Pd nanoparticles. For reported average values, 48 measurements of particles were taken. (K) BF-STEM image showing the amorphous Al2O3 ALD coating. For reported average values, 18 measurements of the Al2O3 coating layer were taken. Joule 2019 3, 2219-2240DOI: (10.1016/j.joule.2019.06.022) Copyright © 2019 Elsevier Inc. Terms and Conditions

Figure 3 Activity of Uncoated and ALD-Coated 0.5 wt % Pd/TiO2 Catalysts during Batch Muconate Hydrogenation Reactions Reaction conditions: 15 mg catalyst, 25 mL 1 wt % muconic acid in ethanol, 24°C, 24 bar H2, stirring at 1,600 rpm. Joule 2019 3, 2219-2240DOI: (10.1016/j.joule.2019.06.022) Copyright © 2019 Elsevier Inc. Terms and Conditions

Figure 4 Partial Conversion TOS Activity and Leaching Stability of the Uncoated and ALD-Coated 0.5 wt % Pd/TiO2 Catalysts during Continuous Muconate Hydrogenation Shaded areas reflect average variance in conversion rate measurements from duplicate reactions. Joule 2019 3, 2219-2240DOI: (10.1016/j.joule.2019.06.022) Copyright © 2019 Elsevier Inc. Terms and Conditions

Figure 5 Sintering and Structural Stability with Thermal Treatment (A and B) STEM-EDS maps of Pd nanoparticles on the thermally treated uncoated (A) and 100-mg ALD-coated (B) 0.5 wt % Pd/TiO2 catalysts. (C and D) Activity of uncoated (C) and 100-mg ALD-coated (D) 0.5 wt % Pd/TiO2 catalysts after oxidative exposure at 700°C for 4 h. Thermal treatment conditions: 700°C under air for 4 h followed by 200°C under hydrogen for 2 h. Reaction conditions: 15 mg catalyst, 25 mL 1 wt % muconic acid in ethanol, 24°C, 24 bar H2, stirring at 1,600 rpm. Joule 2019 3, 2219-2240DOI: (10.1016/j.joule.2019.06.022) Copyright © 2019 Elsevier Inc. Terms and Conditions

Figure 6 Thermal Stability with Repeated Treatments (A) BET surface areas of the uncoated and 10-g ALD-coated 0.5 wt % Pd/TiO2 catalysts over the course of five thermal treatments. (B) CO uptake values of the uncoated and 10-g ALD-coated 0.5 wt % Pd/TiO2 catalysts over the course of five thermal treatments. (C) Adipic acid yield by the uncoated and 10-g ALD-coated 0.5 wt % Pd/TiO2 catalysts over the course of five thermal treatments at t = 35 min during batch muconic acid hydrogenation reactions. (D) Partial conversion TOS activity of the uncoated and 10-g ALD-coated 0.5 wt % Pd/TiO2 catalysts after five thermal treatments. Reaction conditions: 15 mg catalyst, 25 mL 1 wt % muconic acid in ethanol, 24°C, 24 bar H2, stirring at 1,600 rpm. Joule 2019 3, 2219-2240DOI: (10.1016/j.joule.2019.06.022) Copyright © 2019 Elsevier Inc. Terms and Conditions

Figure 7 Process Impacts of ALD Catalysts for an nth-Generation Adipic Acid Biorefinery (A) Simplified block flow diagram for the bio-based adipic acid process model. (B) Impact of catalyst lifetime on bio-adipic acid MSP. (C) Process sensitivity analysis for a 1-year catalyst lifetime baseline scenario. Joule 2019 3, 2219-2240DOI: (10.1016/j.joule.2019.06.022) Copyright © 2019 Elsevier Inc. Terms and Conditions