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Conference Abstracts - Oral Session - O-A1: Bio-mimic Complexes for Hydrogen Storage Using CO2 as a Carrier Wan-Hui Wang, 1,2) Xiujuan Feng 1) and Ming Bao 1,2) 1) State Key Laboratory of Fine Chemicals, Dalian University of Technology, Dalian, 116023, China 2) School of Chemical Engineering, Dalian University of Technology, Panjin, 124221, China Transformation of greenhouse gas CO2 to fuel has attracted much attention because its important contribution to CO2 elimination and development of sustainable energy system. Formic acid (FA) is an important product of CO2 transformation since it can be used in direct FA fuel cell. In addition, it is also a promising hydrogen carrier because it is nontoxic, biodegradable, and liquidus at room temperature. We have designed and synthesized a series of proton-responsive Ir complexes with hydroxyl substituted N,N-bidentate ligands for efficient catalytic interconversion 1,2 between CO2/H2 and formic acid. Herein, we report our recent studies on catalytic CO2 hydrogenation and dehydrogenation of formic acid using novel bio-inspired complexes.3 We have developed proton-responsive Ru pincer complexes for efficient hydrogenation of CO2 to formic acid/formate in water. Pendant OH group was demonstrated to be crucial for H2 heterolytic cleavage and favorable for hydride formation. In addition, we have developed bio-mimic Ir complexes with pendant amine group for FA dehydrogenation. The mechanistic investigation suggests that pendent amine group can significantly promote hydrogen generation via proton shuttle. Reference 1. Wang, W.-H.*; Himeda, Y.*; Muckerman, J. T.*; Manbeck, G. F.; Fujita, E.* Chem. Rev. 2015, 115, 12936. 2. Wang, W.-H.; Ertem, M. Z.; Xu, S.; Onishi, N.; Manaka, Y.; Suna, Y.; Kambayashi, H.; Muckerman, J. T.; Fujita, E.; Himeda, Y.* ACS Catal. 2015, 5, 5496. 3. Wang, W.-H; Wang, H.; Yang, Y.; Lai, X.; Li, Y.;* Wang, J.; Himeda, Y.; Bao, M.* ChemSusChem. 2020, 13, 5015. O-A2: Ir(NHC)-Catalyzed Sustainable Transfer Hydrogenation of CO2 Yeon-Joo Cheong, Hye-Young Jang* Department of Energy Systems Research, Ajou University, Suwon 16499, Korea Transition metal-catalyzed transformation of CO2 to valuable chemicals has received great attention because the consumption of CO2 would reduce CO2 in the air, and the production of chemicals from CO2 would reduce the further consumption of fossil fuel-based carbon sources. In particular, the transfer hydrogenation of CO2 using biomass-derived glycerol has advantages such as sustainability, nontoxicity, and nonvolatility of hydrogen source (glycerol), no use of explosive H2 gas, and the usefulness of byproducts (lactic acid) generated from glycerol. Recently reported transfer hydrogenation of CO2 in glycerol involves ruthenium and iridium-based catalysts modified with N-heterocyclic carbene (NHC). The NHC- modified transition metal catalysts exhibit high catalytic activity and stability under harsh reaction conditions (high temperature and the basic media). In this presentation, we present various iridium catalysts modified with biscarbene and triscarbene ligands and their catalytic activity in the transfer hydrogenation of CO2 in glycerol. O C O Ir catalyst or formate (FA) + lactate (LA) glycerol K2CO3 Ir(biscarbene) catalyst Ir(triscarbene) catalyst R R N N N N N R N N R N - Ir Ir PF6 N - L N - COD X PF6 R N N R N N N N N R Ir N L Ir N - N COD X - Ir(COD)I R PF6 1. Y.-J. Cheong, K. Sung, S. Park, J. Jung, H.-Y. Jang, ACS Sustainable Chem. Eng. 2020, 8, 6972-6978. 2. Y.-J. Cheong, K. Sung, J.-A. Kim, K. Kim, H.-Y.Jang, Eur. J. Inorg. Chem. 2020, 4064-4068. O-A3: Mechanistic Understanding of Tandem Reaction of CO2 Reduction and Ethane Aromatization over Zn/P-ZSM-5 Huahua Fan1, Xiaowa Nie1,*, Xinwen Guo1,* and Chunshan Song1,2,* 1State Key Laboratory of Fine Chemicals, PSU-DUT Joint Center for Energy Research, School of Chemical Engineering, Dalian University of Technology, Dalian, P.R. China 2Department of Chemistry, Faculty of Science, The Chinese University of Hong Kong, Shatin, NT, Hong Kong, P.R. China Conversion of abundant and inexpensive light alkanes to more valuable aromatics is more lucrative and has received extensive attention. Tandem reactions of CO2 reduction and dehydrogenation/aromatization of light alkanes are more efficient and environment-friendly, in which CO2 can assist the catalytic conversion of light alkanes and improve the selectivity of target aromatic products. Modified zeolite can catalyze the dehydrogenation and aromatization of light alkanes coupled with CO2 reduction. The Zn/P-ZSM-5 catalyst that directly converts CO2 and ethane into liquid aromatics with high conversion and selectivity has been developed. The cooperation of CO2 and Zn/P-ZSM-5 inhibits the loss of Zn and significantly suppresses the carbon deposition via CO2-assisted oxidative dehydrogenation/aromatization of ethane over Zn/P-ZSM- 5, therefore enhancing the stability of the catalyst. Reaction pathways of ethane dehydrogenation/aromatization over Zn/ZSM-5 and Zn/P-ZSM-5 are identified by performing density functional theory calculations on the interactions among Zn, P and CO2. P addition increases the barriers for methane formation in the process of ethane dehydrogenation/aromatization over Zn/P-ZSM-5, thus promoting aromatics formation. With Zn/P-ZSM-5, the presence of CO2 can eliminate molecular H2 and consume carbon precursors, suppressing undesired hydrogenolysis and improving the catalyst stability. This work provides fundamental insight into the roles of P and CO2 in promoting ethane dehydrogenation/aromatization to aromatics. O-A6: Boosting light olefin selectivity in CO2 hydrogenation by adding Co to Fe catalysts within close proximity Fei Yuan1, Guanghui Zhang1, Jie Zhu1, Fanshu Ding1, Anfeng Zhang1, Xinwen Guo1,*, Chunshan Song1,2,* 1State Key Laboratory of Fine Chemicals, School of Chemical Engineering, Dalian University of Technology, Dalian, 116024 2Department of Chemistry, the Chinese University of Hong Kong, Shatin, Hong Kong E-mail: [email protected]; [email protected] Fig. 1 The influence of the intimacy between Fe and Co sites on the catalytic performance of CO2 hydrogenation = Direct conversion of carbon dioxide (CO2) into lower olefins (C2-C4 ) is highly attractive as a sustainable production route for its great significance in greenhouse gas emission control and fossil fuel substitution. Fe-based catalysts have been extensively studied in CO2 hydrogenation, which usually show unsatisfactory selectivity toward lower olefins. Here we present a high-dispersion catalyst precursor = CoFe2O4 with Na (Na-CoFe2O4) that offers C2-C4 space time yield as high as 2.88 = -1 -1 μmolC2-C4 gcat s and olefin to paraffin ratio about 6 at CO2 conversion higher than 41%. High dispersion and the intimate contact between Fe and Co sites help inhibit the formation of methane, and favor a higher selectivity of C2+ hydrocarbons, especially lower olefins. The presence of Na further promotes chain growth and suppresses the direct hydrogenation of Fe-(CH2)n intermediates. A superior stability over 100 h was observed, demonstrating the promising potential of this catalyst for industrial applications. References [1] Yuan, F.; Zhang, G.; Zhu, J,; Ding, F.; Zhang, A.; Guo, X.; Song, C.; Guo, X.; Song, C. Catalysis Today, 2021, 371, 142 O-A7: CO2 hydrogenation to C2+ products over TiO2 supported catalysts Canio Scarfiello1,2,3, Katerina Soulantica2, Philippe Serp1, Doan Pham Minh3 1LCC, CNRS-UPR 8241, ENSIACET, Université de Toulouse, France 2LPCNO, Université de Toulouse, CNRS, INSA, UPS, Toulouse, France 3Université de Toulouse, IMT Mines Albi, UMR CNRS 5302, Centre RAPSODEE Albi, France More than 99% of anthropogenic CO2 emissions come from fossil fuels, mainly for energy production [1]. Therefore, CO2 conversion to valuable products is a necessary step toward a sustainable development of our societies. While the hydrogenation to C1 products (CO, CH4, CH3OH, etc.) is relatively well mastered, the production of C2+ molecules is still challenging [2]. The thermocatalytic CO2 hydrogenation to liquid hydrocarbons can be achieved via methanol reaction mechanism [2] or via CO2 modified FTS mechanism [2]. The latter requires two reactions in series: the reverse water gas shift reaction (RWGS) for the initial hydrogenation of CO2 to CO; followed by the Fischer Tropsch synthesis (FTS) for the conversion of CO to C2+. Low temperatures are necessary to favor the exothermic FTS reaction and drive the selectivity towards C2-C4 and C5+ products. However, low temperatures favor methanation (exothermic) and are detrimental to RWGS (endothermic), leading to a series of competitive reactions that can strongly affect the selectivity of the global process. Thus, the main objective of this work is to design a convenient catalyst system which allows performing both steps of CO2 hydrogenation in to C2+ in a fixed- bed reactor. The targeted catalyst system is based on Pd and Co supported on commercial and modified TiO2 supports. The catalysts prepared on an appropriately modified support showed higher activity than those prepared on the commercial support, at temperatures as low as 220 and 250 °C. Moreover, different operating conditions allow modifying the product selectivity toward CO, CH4, C2-C4 and C5+. Under selected conditions, the selectivity to C5+ can be maintained above 50%. [1] IEA, "Global Energy and CO2 Status Report," 2019. [2] Ye, RP., Ding, J., Gong, W. et al. CO2 hydrogenation to high-value products via heterogeneous catalysis. Nat Commun 10, 5698