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1. Reactivity of Pd–MO2 encapsulated catalytic systems for CO oxidation

   https://doi.org/https://doi.org/10.1039/D1CY01916C  

   Herrera L. I. P., Freitas L. (January 2021, Catalysis science technology)

   In this study, we present an investigation aimed at characterizing and understanding the synergistic interactions in encapsulated catalytic structures between the metal core (i.e., Pd) and oxide shell (i.e., TiO2, ZrO2, and CeO2). Encapsulated catalysts were synthesized using a two-step procedure involving the initial colloidal synthesis of Pd nanoparticles (NPs) capped by various ligands and subsequent sol–gel encapsulation of the NPs with porous MO2 (M = Ti, Zr, Ce) shells. The encapsulated catalytic systems displayed higher activity than the Pd/MO2 supported structures due to unique physicochemical properties at the Pd–MO2 interface. Pd@ZrO2 exhibited the highest catalytic activity for CO oxidation. Results also suggested that the active sites in Pd encapsulated by an amorphous ZrO2 shell structure were significantly more active than the crystalline oxide encapsulated structures at low temperatures. Furthermore, CO DRIFTS studies showed that Pd redispersion occurred under CO oxidation reaction conditions and as a function of the oxide shell composition, being observed in Pd@TiO2 systems only, with potential formation of smaller NPs and oxide-supported Pd clusters after reaction. This investigation demonstrated that metal oxide composition and (in some cases) crystallinity play major roles in catalyst activity for encapsulated catalytic systems. 

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2. A General Approach for Metal Nanoparticle Encapsulation Within Porous Oxides

   https://doi.org/10.1002/adma.202409710  

   Zhou, Chengshuang; Oh, Jinwon; Stone, Michael L; Richardson, Sydney; Chung, Pin‐Hung; Osio‐Norgaard, Jorge; Nhan, Bang T; Kumar, Abinash; Chi, Miaofang; Cargnello, Matteo (November 2024, Advanced Materials)

   Abstract Encapsulation of metal nanoparticles within oxide materials has been shown as an effective strategy to improve activity, selectivity, and stability in several catalytic applications. Several approaches have been proposed to encapsulate nanoparticles, such as forming core‐shell structures, growing ordered structures (zeolites or metal‐organic frameworks) on nanoparticles, or directly depositing support materials on nanoparticles. Here, a general nanocasting method is demonstrated that can produce diverse encapsulated metal@oxide structures with different compositions (Pt, Pd, Rh) and multiple types of oxides (Al₂O₃, Al₂O₃‐CeO₂, ZrO₂, ZnZrO_x, In₂O₃, Mn₂O₃, TiO₂) while controlling the size and dispersion of nanoparticles and the porous structure of the oxide. Metal@polymer structures are first prepared, and then the oxide precursor is infiltrated into such structures and the resulting material is calcined to form the metal@oxide structures. Most Pt@oxides catalysts show similar catalytic activity, demonstrating the availability of surface Pt sites in the encapsulated structures. However, the Pt@Mn₂O₃sample showed much higher CO oxidation activity, while also being stable under aging conditions. This work demonstrated a robust nanocasting method to synthesize metal@oxide structures, which can be utilized in catalysis to finely tune metal‐oxide interfaces. 

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3. Ultra-thin ZrO ₂ overcoating on CuO-ZnO-Al ₂ O ₃ catalyst by atomic layer deposition for improved catalytic performance of CO ₂ hydrogenation to dimethyl ether

   https://doi.org/10.1088/1361-6528/acc036  

   Fan, Xiao; Jin, Baitang; He, Xiaoqing; Li, Shiguang; Liang, Xinhua (March 2023, Nanotechnology)

   Abstract An ultra-thin overcoating of zirconium oxide (ZrO 2 ) film on CuO-ZnO-Al 2 O 3 (CZA) catalysts by atomic layer deposition (ALD) was proved to enhance the catalytic performance of CZA/HZSM-5 (H form of Zeolite Socony Mobil-5) bifunctional catalysts for hydrogenation of CO 2 to dimethyl ether (DME). Under optimal reaction conditions (i.e. 240 °C and 2.8 MPa), the yield of product DME increased from 17.22% for the bare CZA/HZSM-5 catalysts, to 18.40% for the CZA catalyst after 5 cycles of ZrO 2 ALD with HZSM-5 catalyst. All the catalysts modified by ZrO 2 ALD displayed significantly improved catalytic stability of hydrogenation of CO 2 to DME reaction, compared to that of CZA/HZSM-5 bifunctional catalysts. The loss of DME yield in 100 h of reaction was greatly mitigated from 6.20% (loss of absolute value) to 3.01% for the CZA catalyst with 20 cycles of ZrO 2 ALD overcoating. Characterizations including hydrogen temperature programmed reduction, x-ray powder diffraction, and x-ray photoelectron spectroscopy revealed that there was strong interaction between Cu active centers and ZrO 2 . 

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4. Benzoquinone Cocatalyst Contributions to DAF/Pd(OAc) ₂ -Catalyzed Aerobic Allylic Acetoxylation in the Absence and Presence of a Co(salophen) Cocatalyst

   https://doi.org/10.1021/acscatal.1c01074  

   Kozack, Caitlin V.; Tereniak, Stephen J.; Jaworski, Jonathan N.; Li, Bao; Bruns, David L.; Knapp, Spring M.; Landis, Clark R.; Stahl, Shannon S. (April 2021, ACS Catalysis)

   null (Ed.)

   Palladium(II)-catalyzed allylic acetoxylation has been the focus of extensive development and investigation. Methods that use molecular oxygen (O2) as the terminal oxidant typically benefit from the use of benzoquinone (BQ) and a transition-metal (TM) cocatalyst, such as Co(salophen), to support oxidation of Pd0 during catalytic turnover. We previously showed that Pd(OAc)2 and 4,5-diazafluoren-9-one (DAF) as an ancillary ligand catalyze allylic oxidation with O2 in the absence of cocatalysts. Herein, we show that BQ enhances DAF/Pd(OAc)2 catalytic activity, nearly matching the performance of reactions that include both BQ and Co(salophen). These observations are complemented by mechanistic studies of DAF/Pd(OAc)2 catalyst systems under three different oxidation conditions: (1) O2 alone, (2) O2 with cocatalytic BQ, and (3) O2 with cocatalytic BQ and Co(salophen). The beneficial effect of BQ in the absence of Co(salophen) is traced to the synergistic roles of O2 and BQ, both of which are capable of oxidizing Pd0 to PdII. The reaction of O2 generates H2O2 as a byproduct, which can oxidize hydroquinone to quinone in the presence of PdII. NMR spectroscopic studies, however, show that hydroquinone is the predominant redox state of the quinone cocatalyst in the absence of Co(salophen), while inclusion of Co(salophen) maintains oxidized quinone throughout the reaction, resulting in better reaction performance. 

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5. Deoxydehydration of 1,4-anhydroerythritol over anatase TiO ₂ (101)-supported ReO _x and MoO _x

   https://doi.org/10.1039/d0cy00434k  

   Xi, Yongjie; Lauterbach, Jochen; Pagan-Torres, Yomaira; Heyden, Andreas (June 2020, Catalysis Science & Technology)

   Heterogeneously catalyzed deoxydehydration (DODH) ordinarily occurs over relatively costly oxide supported ReO x sites and is an effective process for the removal of vicinal OH groups that are common in biomass-derived chemicals. Here, through first-principles calculations, we investigate the DODH of 1,4-anhydroerythritol over anatase TiO 2 (101)-supported ReO x and MoO x . The atomistic structures of ReO x and MoO x under typical reaction conditions were identified with constrained thermodynamics calculations as ReO 2 (2O)/6H–TiO 2 and MoO(2O)/3H–TiO 2 , respectively. The calculated energy profile and developed microkinetic reaction model suggest that both ReO 2 (2O)/6H–TiO 2 and MoO(2O)/3H–TiO 2 exhibit a relatively low DODH activity at 413 K. However, at higher temperatures such as 473 K, MoO(2O)/TiO 2 (101) was found to exhibit a reasonably high catalytic activity similar to ReO 2 (2O)/6H–TiO 2 , consistent with a recent experimental study. Mechanistically, the first O–H bond cleavage of 1,4-anhydroerythritol and the dihydrofuran extrusion were found to be the rate-controlling steps for the reaction over ReO 2 (2O)/6H–TiO 2 and MoO(2O)/3H–TiO 2 , respectively. Thus, this study clarifies the mechanism of the DODH over oxide-supported catalysts and provides meaningful insight into the design of low-cost DODH catalysts. 

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