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1

Anjali, A. Ingle, Z. Ansari Shahid, Z. Shende Diwakar, L. Wasewar Kailas, and B. Pandit Aniruddha. "Hydrogenation of 2-ethylanthraquinone with Pd supported on hollow ceramic microsphere catalyst: An experimental and kinetic study." Journal of Indian Chemical Society Vol. 97, Jul 2020 (2020): 1033–37. https://doi.org/10.5281/zenodo.5667863.

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Chemical Engineering Department, Vidyasagar National Institute of Technology Nagpur, Nagpur-440 010, Maharashtra, India Department of Chemical Engineering, Institute of Chemical Technology, Mumbai-40019, India <em>E-mail</em>: ab.pandit@ictmumbai.edu.in <em>Manuscript received online 10 April 2020, accepted 08 June 2020</em> The catalytic hydrogenation of 2-ethylanthraquinone in the anthraquinone process of production of hydrogen peroxide gaining more interest to meet environmental demands of hydrogen peroxide as green oxidant. Noble metal palladium becomes a new category of catalyst due to their significant applicability in the catalytic hydrogenation reactions. Herein, wet impregnation method was used for synthesis of palladium supported on hollow ceramic microsphere catalysts. The palladium supported on hollow ceramic microsphere exhibits high catalytic selectivity, activity and stability in the liquid phase hydrogenation of 2- ethylanthraquinone. The reaction obeyed zero and first order kinetics with 2-ethylanthraquinone and hydrogen respectively. The average value of reaction rate constant observed was 2 mol L<sup>&ndash;1</sup> h<sup>&ndash;1</sup> and 6 L h<sup>&ndash;1</sup> respectively. Highest yield of hydrogen peroxide obtained was 96.5% with a less consumption of 2-ethylanthraquinone.
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2

Drelinkiewicz, A., R. Laitinen, R. Kangas, and J. Pursiainen. "2-Ethylanthraquinone hydrogenation on Pd/Al2O3." Applied Catalysis A: General 284, no. 1-2 (2005): 59–67. http://dx.doi.org/10.1016/j.apcata.2005.01.018.

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3

Zhang, Jinli, Kaige Gao, Suli Wang, Wei Li, and You Han. "Performance of bimetallic PdRu catalysts supported on gamma alumina for 2-ethylanthraquinone hydrogenation." RSC Advances 7, no. 11 (2017): 6447–56. http://dx.doi.org/10.1039/c6ra26142f.

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4

Yao, Hongbao, Chun Shen, Yujun Wang, and Guangsheng Luo. "Catalytic hydrogenation of 2-ethylanthraquinone using an in situ synthesized Pd catalyst." RSC Advances 6, no. 28 (2016): 23942–48. http://dx.doi.org/10.1039/c5ra23187f.

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Catalytic performance of anin situprepared Pd catalyst with egg–shell structure, which can weaken internal diffusion resistance effectively demonstrated by Thiele module values, was studied in detail for the hydrogenation of 2-ethylanthraquinone.
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5

Han, You, Zhiyuan He, Suli Wang, Wei Li, and Jinli Zhang. "Performance of facet-controlled Pd nanocrystals in 2-ethylanthraquinone hydrogenation." Catalysis Science & Technology 5, no. 5 (2015): 2630–39. http://dx.doi.org/10.1039/c5cy00050e.

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6

Drelinkiewicz, A., R. Kangas, R. Laitinen, A. Pukkinen, and J. Pursiainen. "Hydrogenation of 2-ethylanthraquinone on alumina-supported palladium catalysts." Applied Catalysis A: General 263, no. 1 (2004): 71–82. http://dx.doi.org/10.1016/j.apcata.2003.12.010.

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7

Wang, Feng, Xianlun Xu та Kunpeng Sun. "Hydrogenation of 2-ethylanthraquinone over Pd/Zro2-γ-Al2O3 catalyst". Reaction Kinetics and Catalysis Letters 93, № 1 (2008): 135–40. http://dx.doi.org/10.1007/s11144-008-5218-5.

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8

Drelinkiewicz, A., M. Hasik, and M. Kloc. "Liquid-Phase Hydrogenation of 2-Ethylanthraquinone over Pd/Polyaniline Catalysts." Journal of Catalysis 186, no. 1 (1999): 123–33. http://dx.doi.org/10.1006/jcat.1999.2493.

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9

Santacesaria, E., M. Di Serio, R. Velotti, and U. Leone. "Hydrogenation of the aromatic rings of 2-ethylanthraquinone on palladium catalyst." Journal of Molecular Catalysis 94, no. 1 (1994): 37–46. http://dx.doi.org/10.1016/0304-5102(94)87028-4.

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10

Zhang, Jianguo, Defu Li, Yujun Zhao, Qingdan Kong, and Shudong Wang. "A Pd/Al2O3/cordierite monolithic catalyst for hydrogenation of 2-ethylanthraquinone." Catalysis Communications 9, no. 15 (2008): 2565–69. http://dx.doi.org/10.1016/j.catcom.2008.07.012.

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11

Zhang, Yue, Zhiyong Pan, Nan Wang, and Li Wang. "Performance of carbon-modified Pd/SBA-15 catalyst for 2-ethylanthraquinone hydrogenation." Molecular Catalysis 504 (March 2021): 111424. http://dx.doi.org/10.1016/j.mcat.2021.111424.

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12

Li, Xiaotong, Hongjiu Su, Dawei Li, Haijun Chen, Xiaoye Yang, and Shudong Wang. "Highly dispersed Pd/AlPO-5 catalyst for catalytic hydrogenation of 2-ethylanthraquinone." Applied Catalysis A: General 528 (November 2016): 168–74. http://dx.doi.org/10.1016/j.apcata.2016.10.007.

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13

Guo, Yanyan, Chengna Dai, and Zhigang Lei. "Hydrogenation of 2-ethylanthraquinone with monolithic catalysts: An experimental and modeling study." Chemical Engineering Science 172 (November 2017): 370–84. http://dx.doi.org/10.1016/j.ces.2017.06.032.

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14

Drelinkiewicz, Alicja, Anna Waksmundzka-Góra, Wacław Makowski, and Jaroslav Stejskal. "Pd/polyaniline(SiO2) a novel catalyst for the hydrogenation of 2-ethylanthraquinone." Catalysis Communications 6, no. 5 (2005): 347–56. http://dx.doi.org/10.1016/j.catcom.2005.02.009.

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15

Hong, Runrun, Yufei He, Chenglin Miao, Junting Feng, and Dianqing Li. "Fabrication of Supported Pd–Ir Mesocrystal Catalyst for Hydrogenation of 2-Ethylanthraquinone." Catalysis Letters 147, no. 7 (2017): 1802–10. http://dx.doi.org/10.1007/s10562-017-2076-7.

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16

Liu, Bo, Minghua Qiao, Jianqiang Wang, and Kangnian Fan. "Highly selective amorphous Ni–Cr–B catalyst in 2-ethylanthraquinone hydrogenation to 2-ethylanthrahydroquinone." Chemical Communications, no. 11 (May 7, 2002): 1236–37. http://dx.doi.org/10.1039/b202499n.

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17

Guo, Yanyan, Chengna Dai, and Zhigang Lei. "Hydrogenation of 2-ethylanthraquinone with bimetallic monolithic catalysts: An experimental and DFT study." Chinese Journal of Catalysis 39, no. 6 (2018): 1070–80. http://dx.doi.org/10.1016/s1872-2067(18)63035-9.

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18

Chen, Xueying, Shuai Wang, Jihua Zhuang, Minghua Qiao, Kangnian Fan, and Heyong He. "Mesoporous silica-supported NiB amorphous alloy catalysts for selective hydrogenation of 2-ethylanthraquinone." Journal of Catalysis 227, no. 2 (2004): 419–27. http://dx.doi.org/10.1016/j.jcat.2004.08.002.

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19

Drelinkiewicz, Alicja. "Deep hydrogenation of 2-ethylanthraquinone over Pd/SiO2 catalyst in the liquid phase." Journal of Molecular Catalysis 75, no. 3 (1992): 321–32. http://dx.doi.org/10.1016/0304-5102(92)80134-3.

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20

Drelinkiewicz, A. "Kinetic aspects in the selectivity of deep hydrogenation of 2-ethylanthraquinone overPd/SiO2." Journal of Molecular Catalysis A: Chemical 101, no. 1 (1995): 61–74. http://dx.doi.org/10.1016/1381-1169(95)00048-8.

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21

Liu, Dingsheng, Jianguo Zhang, Defu Li, Qingdan Kong, Tong Zhang, and Shudong Wang. "Hydrogenation of 2-ethylanthraquinone under Taylor flow in single square channel monolith reactors." AIChE Journal 55, no. 3 (2009): 726–36. http://dx.doi.org/10.1002/aic.11696.

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22

Hong, Runrun, Yufei He, Junting Feng, and Dianqing Li. "Fabrication of supported Pd–Ir/Al 2 O 3 bimetallic catalysts for 2‐ethylanthraquinone hydrogenation." AIChE Journal 63, no. 9 (2017): 3955–65. http://dx.doi.org/10.1002/aic.15748.

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23

Hou, Yongjiang, Yaquan Wang, Fei He, et al. "Liquid phase hydrogenation of 2-ethylanthraquinone over La-doped Ni–B amorphous alloy catalysts." Materials Letters 58, no. 7-8 (2004): 1267–71. http://dx.doi.org/10.1016/j.matlet.2003.09.019.

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24

Yuan, Enxian, Xiangwei Ren, Li Wang, and Wentao Zhao. "A comparison of the catalytic hydrogenation of 2-amylanthraquinone and 2-ethylanthraquinone over a Pd/Al2O3 catalyst." Frontiers of Chemical Science and Engineering 11, no. 2 (2017): 177–84. http://dx.doi.org/10.1007/s11705-016-1604-0.

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25

FANG, J., X. CHEN, B. LIU, et al. "Liquid-phase chemoselective hydrogenation of 2-ethylanthraquinone over chromium-modified nanosized amorphous Ni–B catalysts." Journal of Catalysis 229, no. 1 (2005): 97–104. http://dx.doi.org/10.1016/j.jcat.2004.10.014.

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26

Wang, Yunhao, Kaige Gao, Chenliang Ye, Ang Li, Cuili Guo, and Jinli Zhang. "Highly Dispersed Pd Nanoparticles Supported on Zr-Doped MgAl Mixed Metal Oxides for 2-Ethylanthraquinone Hydrogenation." Transactions of Tianjin University 25, no. 6 (2019): 576–85. http://dx.doi.org/10.1007/s12209-019-00203-0.

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27

Shi, Xin, Enxian Yuan, Guozhu Liu, and Li Wang. "Effects of porous oxide layer on performance of Pd-based monolithic catalysts for 2-ethylanthraquinone hydrogenation." Chinese Journal of Chemical Engineering 24, no. 11 (2016): 1570–76. http://dx.doi.org/10.1016/j.cjche.2016.04.032.

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28

Biffis, Andrea, Rossana Ricoveri, Sandro Campestrini, Milan Kralik, Karel Jeřàbek, and Benedetto Corain. "Highly Chemoselective Hydrogenation of 2-Ethylanthraquinone to 2-Ethylanthrahydroquinone Catalyzed by Palladium Metal Dispersed inside Highly Lipophilic Functional Resins." Chemistry - A European Journal 8, no. 13 (2002): 2962. http://dx.doi.org/10.1002/1521-3765(20020703)8:13<2962::aid-chem2962>3.0.co;2-5.

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29

Bi, Ruxia, Qian Wang, Chenglin Miao, Junting Feng, and Dianqing Li. "Pd/NiO/Al Array Catalyst for 2-Ethylanthraquinone Hydrogenation: Synergistic Effect Between Pd and NiO/Al Support." Catalysis Letters 149, no. 5 (2019): 1286–96. http://dx.doi.org/10.1007/s10562-019-02712-y.

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30

Hou, Yongjiang, Yaquan Wang, and Zhentao Mi. "The beneficial effects of molybdenum addition on Ni–B amorphous alloy catalyst used in 2-ethylanthraquinone hydrogenation." Journal of Materials Science 40, no. 24 (2005): 6585–88. http://dx.doi.org/10.1007/s10853-005-4223-6.

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31

Guo, Yanyan, Chengna Dai, and Zhigang Lei. "Hydrogenation of 2-ethylanthraquinone on Pd-La/SiO2/cordierite and Pd-Zn/SiO2/cordierite bimetallic monolithic catalysts." Chemical Engineering and Processing - Process Intensification 136 (February 2019): 211–25. http://dx.doi.org/10.1016/j.cep.2018.11.006.

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32

Liu, Bo, Minghua Qiao, Jing-Fa Deng, Kangnian Fan, Xiaoxin Zhang, and Baoning Zong. "Skeletal Ni Catalyst Prepared from a Rapidly Quenched Ni–Al Alloy and Its High Selectivity in 2-Ethylanthraquinone Hydrogenation." Journal of Catalysis 204, no. 2 (2001): 512–15. http://dx.doi.org/10.1006/jcat.2001.3405.

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33

Santacesaria, E., M. Di Serio, R. Velotti, and U. Leone. "Erratum to ‘Hydrogenation of the aromatic rings of 2-ethylanthraquinone on palladium catalyst’ [J. Mol. Catal. 94 (1994) 37]." Journal of Molecular Catalysis A: Chemical 99, no. 3 (1995): 151. http://dx.doi.org/10.1016/1381-1169(95)00081-x.

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34

Chen, X. "Selective hydrogenation of 2-ethylanthraquinone over an environmentally benign Ni_B/SBA-15 catalyst prepared by a novel reductant–impregnation method." Journal of Catalysis 220, no. 1 (2003): 254–57. http://dx.doi.org/10.1016/j.jcat.2003.07.007.

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35

Drelinkiewicz, A., A. Pukkinen, R. Kangas, and R. Laitinen. "Hydrogenation of 2-Ethylanthraquinone over Pd/SiO2and Pd/Al2O3in the Fixed-Bed Reactor. The Effect of the Type of Support." Catalysis Letters 94, no. 3/4 (2004): 157–70. http://dx.doi.org/10.1023/b:catl.0000020540.90536.6d.

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36

Guo, Yanyan, Yichun Dong, Zhigang Lei, Zhixue Liu, and Jiqin Zhu. "High-performance Pd-N (N = Ga or Ag) bimetallic monolithic catalyst for the hydrogenation of 2-ethylanthraquinone: Experimental and DFT studies." Molecular Catalysis 509 (June 2021): 111604. http://dx.doi.org/10.1016/j.mcat.2021.111604.

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37

CHEN, Xueying, Minghua QIAO, and Heyong HE. "Effects of Supports on Catalytic Properties of the Supported Ni-B Catalysts for Selective Hydrogenation of 2-Ethylanthraquinone to H2O2." CHINESE JOURNAL OF CATALYSIS (CHINESE VERSION) 32, no. 2 (2011): 325–32. http://dx.doi.org/10.3724/sp.j.1088.2011.00941.

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38

You, HAN, HE Zhi-Yuan, GUAN Yong-Chuan, LI Wei, and ZHANG Jin-Li. "Catalytic Performance of PdAu/Al2O3 Catalyst with Special Structural and Electronic Properties in the 2-Ethylanthraquinone Hydrogenation Reaction." Acta Physico-Chimica Sinica 31, no. 4 (2015): 729–37. http://dx.doi.org/10.3866/pku.whxb201501292.

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39

HU, H., F. XIE, Y. PEI, et al. "Skeletal Ni catalysts prepared from Ni–Al alloys rapidly quenched at different rates: Texture, structure and catalytic performance in chemoselective hydrogenation of 2-ethylanthraquinone." Journal of Catalysis 237, no. 1 (2006): 143–51. http://dx.doi.org/10.1016/j.jcat.2005.11.001.

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40

Liu, G., and Z. Mi. "Hydrogenation of 2-Ethylanthraquinones in a Periodically Operated Trickle-Bed Reactor." Chemical Engineering & Technology 28, no. 8 (2005): 857–62. http://dx.doi.org/10.1002/ceat.200407151.

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41

Wang, Yunhao, Mao Peng, Chenliang Ye, Changna Gan, Jinli Zhang, and Cuili Guo. "Enhanced catalytic performance of Pd‐Ga bimetallic catalysts for 2‐ethylanthraquinone hydrogenation." Applied Organometallic Chemistry, July 2, 2019. http://dx.doi.org/10.1002/aoc.5076.

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42

Ingle, Anjali A., Shahid Z. Ansari, Diwakar Z. Shende, Kailas L. Wasewar, and Aniruddha B. Pandit. "Palladium supported on nano-hybrid Zr–Al–La catalyst for hydrogenation of 2-ethylanthraquinone." Indian Chemical Engineer, April 8, 2020, 1–15. http://dx.doi.org/10.1080/00194506.2020.1749141.

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43

Li, Xiaolei, Tiantong Zhang, Fuying Wang, et al. "Ionic Liquids Boost Anthraquinone Hydrogenation over Pd‐based Bimetallic Pincer Catalysts." ChemCatChem, May 13, 2024. http://dx.doi.org/10.1002/cctc.202400546.

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A series of bimetallic‐ionic liquid (IL) pincer catalysts Pd‐M@IL were synthesized using low Pd‐loading amount (0.3%) and adopting six kinds of ion liquids with the cation containing the imidazole ring, and then evaluated the catalytic activities toward 2‐ethylanthraquinone hydrogenation reaction with the purpose to produce H2O2. Under the reaction conditions of 60 ℃, 0.30 MPa and 15 min reaction time, over the catalysts Pd‐La@[BMIm]Ac/alu and Pd‐La@[VBIM]Br/alu achieved high hydrogenation efficiency(9.4 g/L and 8.5 g/L) but also high selectivity toward the active anthraquinone (98.9% and 99.6%). Through characterizations of STEM, TPD, in‐situ XPS, etc., it illustrates that the pincer catalysts Pd‐La@[BMIm]Ac/alu and Pd‐La@[VBIM]Br/alu have much better dispersity than the bimetallic Pd‐La/alu, these two ionic liquids of [BMIm]Ac and [VBIM]Br provide different local environment around Pd‐La sites, which in turn modulate the catalytic activity of the pincer‐catalysts toward anthraquinone hydrogenation. DFT calculations disclose the unique electron transfer between ILs ([BMIm]Ac and [VBIM]Br) and Pd‐La clusters and subsequent changes of energy barriers for anthraquinone hydrogenation. The work illuminates a facile strategy to design novel hydrogenation catalysts through combining the pincer microenvironment partially encapsulated by the cation and the anion of ionic liquids with the internal bimetallic sites.
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44

Ingle, Anjali A., Diwakar Z. Shende, and Kailas L. Wasewar. "Synthesis, Characterization, and Application of Hollow Ceramic Microsphere based Pd Catalyst for Hydrogenation of 2-ethylanthraquinone." Journal of the Indian Chemical Society, September 2021, 100177. http://dx.doi.org/10.1016/j.jics.2021.100177.

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45

Zhang, Yue, Rongrong Zhang, Shuzhen Lyu, Xiangwei Ren, Guozhu Liu, and Li Wang. "Highly dispersed Pd nanoparticles supported on SBA‐15@derived C from RF resin for hydrogenation of 2‐ethylanthraquinone." AIChE Journal, April 15, 2025. https://doi.org/10.1002/aic.18862.

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AbstractSupported Pd‐based nanoparticles are widely regarded as the most effective catalysts for 2‐ethylthraquinone hydrogenation. Herein, the heteroenergetic dual‐supports were prepared by coating resorcinol‐formaldehyde (RF) resin on mesoporous SBA‐15 to regulate the growth and surface microenvironment of Pd. After calcination and reduction, phenolic hydroxyl groups in the residual carbon layer effectively reduced the Pd particle size, induced the formation of adjacent Pd0–Pdδ+, and created hydrophobicity. Density functional theory calculations revealed that Pd atoms preferentially interact with OH on C, rather than with OH on SBA‐15, providing an intrinsic driving force for smaller Pd particle size. The mass ratio of RF to SBA‐15 was shown to be a crucial parameter affecting the catalytic performance. At the ratio of 4 (carbon content of 2.02%) the catalyst possesses the smallest Pd particles, 30% Pdδ+ proportion, and higher hydrophobicity, achieving the best catalytic performance, with an activity of 0.57 molH2·gPd−1·min−1 and a selectivity of 95.3%.
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46

Li, Jiale, Guandong Wu, Xingye Lin, et al. "Improving the Hydrogenation Performance of Nano‐Catalysts by Constructing a Cavity‐Constrained Fluidized System." Small, February 21, 2025. https://doi.org/10.1002/smll.202410666.

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AbstractNano‐catalysts demonstrate exceptional performance in heterogeneous reactions, yet their potential is often underutilized due to a lack of attention to engineering design. In this study, an innovative encapsulated structure is presented for nano‐catalysts and a corresponding catalytic system. Using an oil‐in‐water droplet strategy, millimeter‐sized hollow spherical alumina (Al2O3‐HS) is fabricated with an average diameter of ≈3 mm and a hollow void size of ≈1 mm. This approach enables the one‐step encapsulation of nanoscale Pd/Al2O3 within the Al2O3‐HS. The resulting assembly is immobilized within a tubular reactor for the hydrogenation of 2‐ethylanthraquinone, with hydrogen introduced from the bottom of the reactor. Remarkably, the encapsulated catalyst achieved twice the H2O2 productivity of conventional supported catalysts. This enhancement is attributed to the cavity‐constrained fluidization behavior of Pd/Al2O3 within the hollow alumina spheres. The design introduces a novel catalytic system that combines shell‐immobilization with the fluidization of encapsulated nano‐catalysts. As the gas velocity exceeds the minimum fluidization velocity, the Pd/Al2O3 particles remain highly accessible while allowing efficient gas and product flow. This hybrid approach integrates the advantages of fixed‐bed and fluidized‐bed systems, offering a promising solution to the technical challenges limiting the industrial application of nano‐catalysts.
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