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1

Li, Lichun, Xiangcan Chen, Chu Yao, and Meng Xu. "Integrated CO2 Capture and Hydrogenation to Produce Formate in Aqueous Amine Solutions Using Pd-Based Catalyst." Catalysts 12, no. 8 (August 21, 2022): 925. http://dx.doi.org/10.3390/catal12080925.

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Integrated CO2 capture and hydrogenation to produce formate offers a sustainable approach for reducing carbon dioxide emissions and producing liquid hydrogen carriers (formate) simultaneously. In the current study, three different types of aqueous amine solutions including monoethanolamine (MEA), diethanolamine (DEA) and triethanolamine (TEA) were investigated as CO2-capturing and hydrogenation agents in the presence of a Pd/NAC catalyst. The effect of amine structures on the CO2 absorption products and formate yield was investigated thoroughly. It was found that the formate product was successfully produced in the presence of all three aqueous amine solutions, with tertiary amine TEA accounting for the highest formate yield under the same CO2 loadings. This is due to the fact that primary and secondary amine moieties in MEA and DEA are responsible for the formation of CO2 adducts of carbamate and bicarbonate, whereas the tertiary amine moiety in TEA is responsible for the formation of hydrogenation-favorable bicarbonate as the solo CO2 absorption product. A high yield of formate of 82.6% was achieved when hydrogenating 3 M TEA with 0.3 mol CO2/mol amine solution in the presence of a Pd/NAC catalyst. In addition, the physio-chemical properties of the Pd/NAC catalyst analyzed using TEM, XRD and XPS characterization were applied to rationalize the superior catalytic performance of the catalyst. The reaction mechanism of integrated CO2 capture and hydrogenation to produce formate in aqueous amine solutions over Pd/NAC catalyst was proposed as well.
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2

Federsel, Christopher, Ralf Jackstell, Albert Boddien, Gabor Laurenczy, and Matthias Beller. "Ruthenium-Catalyzed Hydrogenation of Bicarbonate in Water." ChemSusChem 3, no. 9 (July 15, 2010): 1048–50. http://dx.doi.org/10.1002/cssc.201000151.

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3

Heltzel, Jacob M., Matthew Finn, Diana Ainembabazi, Kai Wang, and Adelina M. Voutchkova-Kostal. "Transfer hydrogenation of carbon dioxide and bicarbonate from glycerol under aqueous conditions." Chemical Communications 54, no. 48 (2018): 6184–87. http://dx.doi.org/10.1039/c8cc03157f.

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Анотація:
Catalytic transfer hydrogenation of CO2 from glycerol to afford formic and lactic acid is an attractive path to valorizing two waste streams. The process is significantly more thermodynamically favorable than direct CO2 hydrogenation.
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4

Heltzel, Jacob M., Matthew Finn, Diana Ainembabazi, Kai Wang, and Adelina M. Voutchkova-Kostal. "Correction: Transfer hydrogenation of carbon dioxide and bicarbonate from glycerol under aqueous conditions." Chemical Communications 56, no. 19 (2020): 2956. http://dx.doi.org/10.1039/d0cc90084b.

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5

Chatterjee, Debabrata, and Papiya Sarkar. "RuIII(edta) catalyzed hydrogenation of bicarbonate to formate." Journal of Coordination Chemistry 69, no. 4 (January 1, 2016): 650–55. http://dx.doi.org/10.1080/00958972.2015.1125476.

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6

Jin, Binbin, Xin Ye, Heng Zhong, and Fangming Jin. "Light-Driven Hydrogenation of Bicarbonate into Formate over Nano-Pd/TiO2." ACS Sustainable Chemistry & Engineering 8, no. 17 (April 16, 2020): 6798–805. http://dx.doi.org/10.1021/acssuschemeng.0c01616.

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7

Sordakis, Katerina, Antonella Guerriero, Hervé Bricout, Maurizio Peruzzini, Paul J. Dyson, Eric Monflier, Frédéric Hapiot, Luca Gonsalvi, and Gábor Laurenczy. "Homogenous catalytic hydrogenation of bicarbonate with water soluble aryl phosphine ligands." Inorganica Chimica Acta 431 (May 2015): 132–38. http://dx.doi.org/10.1016/j.ica.2014.10.034.

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8

WIENER, H. "The heterogeneous catalytic hydrogenation of bicarbonate to formate in aqueous solutions." Journal of Catalysis 110, no. 1 (March 1988): 184–90. http://dx.doi.org/10.1016/0021-9517(88)90308-9.

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9

Ziebart, Carolin, Christopher Federsel, Pazhamalai Anbarasan, Ralf Jackstell, Wolfgang Baumann, Anke Spannenberg, and Matthias Beller. "Well-Defined Iron Catalyst for Improved Hydrogenation of Carbon Dioxide and Bicarbonate." Journal of the American Chemical Society 134, no. 51 (December 11, 2012): 20701–4. http://dx.doi.org/10.1021/ja307924a.

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10

Bosquain, Sylvain S., Antoine Dorcier, Paul J. Dyson, Mikael Erlandsson, Luca Gonsalvi, Gábor Laurenczy, and Maurizio Peruzzini. "Aqueous phase carbon dioxide and bicarbonate hydrogenation catalyzed by cyclopentadienyl ruthenium complexes." Applied Organometallic Chemistry 21, no. 11 (2007): 947–51. http://dx.doi.org/10.1002/aoc.1317.

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11

Coufourier, Sébastien, Sylvain Gaillard, Guillaume Clet, Christian Serre, Marco Daturi, and Jean-Luc Renaud. "A MOF-assisted phosphine free bifunctional iron complex for the hydrogenation of carbon dioxide, sodium bicarbonate and carbonate to formate." Chemical Communications 55, no. 34 (2019): 4977–80. http://dx.doi.org/10.1039/c8cc09771b.

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12

Sato, Yasuhiro, Yoshihito Kayaki, and Takao Ikariya. "Transfer hydrogenation of carbon dioxide via bicarbonate promoted by bifunctional C–N chelating Cp*Ir complexes." Chemical Communications 56, no. 73 (2020): 10762–65. http://dx.doi.org/10.1039/d0cc04379f.

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Анотація:
Metal–NH cooperative Ir complexes having a C–N chelate effectively promoted the reduction of bicarbonate and half-carbonate salts formed from CO2 in 2-propanol under mild conditions to produce formate salts with a maximum turnover number of 3200.
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13

Elek, János, Debby Mangelings, Ferenc Joó, and Yvan Vander Heyden. "Chemometric modelling of the catalytic hydrogenation of bicarbonate to formate in aqueous media." Reaction Kinetics and Catalysis Letters 83, no. 2 (2004): 321–28. http://dx.doi.org/10.1023/b:reac.0000046093.94769.93.

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14

Lee, Li-Chen, Xiaoyu Xing, and Yan Zhao. "Environmental Engineering of Pd Nanoparticle Catalysts for Catalytic Hydrogenation of CO2 and Bicarbonate." ACS Applied Materials & Interfaces 9, no. 44 (October 24, 2017): 38436–44. http://dx.doi.org/10.1021/acsami.7b10591.

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15

Marcos, Rocío, Liqin Xue, Rocío Sánchez-de-Armas, and Mårten S. G. Ahlquist. "Bicarbonate Hydrogenation Catalyzed by Iron: How the Choice of Solvent Can Reverse the Reaction." ACS Catalysis 6, no. 5 (April 7, 2016): 2923–29. http://dx.doi.org/10.1021/acscatal.6b00071.

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16

Drake, Jessica L., Cesar M. Manna, and Jeffery A. Byers. "Enhanced Carbon Dioxide Hydrogenation Facilitated by Catalytic Quantities of Bicarbonate and Other Inorganic Salts." Organometallics 32, no. 23 (November 12, 2013): 6891–94. http://dx.doi.org/10.1021/om401057p.

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17

Thai, Trieu-Tien, Delphine S. Mérel, Albert Poater, Sylvain Gaillard, and Jean-Luc Renaud. "Highly Active Phosphine-Free Bifunctional Iron Complex for Hydrogenation of Bicarbonate and Reductive Amination." Chemistry - A European Journal 21, no. 19 (March 24, 2015): 7066–70. http://dx.doi.org/10.1002/chem.201500720.

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18

Liu, Qiang, Lipeng Wu, Samet Gülak, Nils Rockstroh, Ralf Jackstell, and Matthias Beller. "Towards a Sustainable Synthesis of Formate Salts: Combined Catalytic Methanol Dehydrogenation and Bicarbonate Hydrogenation." Angewandte Chemie International Edition 53, no. 27 (May 28, 2014): 7085–88. http://dx.doi.org/10.1002/anie.201400456.

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19

Joó, Ferenc. "A Breakthrough in Sustainable Production of Formate Salts: Combined Catalytic Methanol Dehydrogenation and Bicarbonate Hydrogenation." ChemCatChem 6, no. 12 (September 26, 2014): 3306–8. http://dx.doi.org/10.1002/cctc.201402591.

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20

Sivanesan, Dharmalingam, Bongkuk Seo, Choong-Sun Lim, and Hyeon-Gook Kim. "Facile hydrogenation of bicarbonate to formate in aqueous medium by highly stable nickel-azatrane complex." Journal of Catalysis 382 (February 2020): 121–28. http://dx.doi.org/10.1016/j.jcat.2019.12.020.

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21

Wang, Jixiao, ChuanCheng Zhou, Zhanming Gao, Xiujuan Feng, Yoshinori Yamamoto, and Ming Bao. "Unsupported Nanoporous Palladium Catalyst for Highly Selective Hydrogenation of Carbon Dioxide and Sodium Bicarbonate into Formate." ChemCatChem 13, no. 11 (April 26, 2021): 2702–8. http://dx.doi.org/10.1002/cctc.202100148.

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22

Thai, Trieu-Tien, Delphine S. Merel, Albert Poater, Sylvain Gaillard, and Jean-Luc Renaud. "ChemInform Abstract: Highly Active Phosphine-Free Bifunctional Iron Complex for Hydrogenation of Bicarbonate and Reductive Amination." ChemInform 46, no. 37 (August 27, 2015): no. http://dx.doi.org/10.1002/chin.201537042.

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23

Krishna, Racharla, Chowdam Ramakrishna, Keshav Soni, Thakkallapalli Gopi, Gujarathi Swetha, Bijendra Saini, and S. Chandra Shekar. "Effect of Alkali Carbonate/Bicarbonate on Citral Hydrogenation over Pd/Carbon Molecular Sieves Catalysts in Aqueous Media." Modern Research in Catalysis 05, no. 01 (2016): 1–10. http://dx.doi.org/10.4236/mrc.2016.51001.

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24

Szatmári, Imre, Gábor Papp, Ferenc Joó, and Ágnes Kathó. "Promoter effect of bicarbonate in hydrogenation of cinnamaldehyde catalyzed by a water-soluble Ru(II)-phosphine complex." Inorganica Chimica Acta 472 (March 2018): 302–6. http://dx.doi.org/10.1016/j.ica.2017.06.061.

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25

Joo, Ferenc. "ChemInform Abstract: A Breakthrough in Sustainable Production of Formate Salts: Combined Catalytic Methanol Dehydrogenation and Bicarbonate Hydrogenation." ChemInform 46, no. 9 (February 16, 2015): no. http://dx.doi.org/10.1002/chin.201509339.

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26

Wu, Yingquan, Li Tan, Tao Zhang, Hongjuan Xie, Guohui Yang, Noritatsu Tsubaki, and Jiangang Chen. "Effect of Preparation Method on ZrO2-Based Catalysts Performance for Isobutanol Synthesis from Syngas." Catalysts 9, no. 9 (September 6, 2019): 752. http://dx.doi.org/10.3390/catal9090752.

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Анотація:
Two types of amorphous ZrO2 (am-ZrO2) catalysts were prepared by different co-precipitation/reflux digestion methods (with ethylenediamine and ammonia as the precipitant respectively). Then, copper and potassium were introduced for modifying ZrO2 via an impregnation method to enhance the catalytic performance. The obtained catalysts were further characterized by means of Brunauer-Emmett-Teller surface areas (BET), X-ray diffraction (XRD), H2-temperature-programmed reduction (H2-TPR), and In situ diffuse reflectance infrared spectroscopy (in situ DRIFTS). CO hydrogenation experiments were performed in a fixed-bed reactor for isobutanol synthesis. Great differences were observed on the distribution of alcohols over the two types of ZrO2 catalysts, which were promoted with the same content of Cu and K. The selectivity of isobutanol on K-CuZrO2 (ammonia as precipitant, A-KCZ) was three times higher than that on K-CuZrO2 (ethylenediamine as precipitant, E-KCZ). The characterization results indicated that the A-KCZ catalyst supplied more active hydroxyls (isolated hydroxyls) for anchoring and dispersing Cu. More importantly, it was found that bicarbonate species were formed, which were ascribed as important C1 species for isobutanol formation on the A-KCZ catalyst surface. These C1 intermediates had relatively stronger adsorption strength than those adsorbed on the E-KCZ catalyst, indicating that the bicarbonate species on the A-KCZ catalyst had a longer residence time for further carbon chain growth. Therefore, the selectivity of isobutanol was greatly enhanced. These findings would extend the horizontal of direct alcohols synthesis from syngas.
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27

Elek, János, Levente Nádasdi, Gábor Papp, Gábor Laurenczy, and Ferenc Joó. "Homogeneous hydrogenation of carbon dioxide and bicarbonate in aqueous solution catalyzed by water-soluble ruthenium(II) phosphine complexes." Applied Catalysis A: General 255, no. 1 (November 2003): 59–67. http://dx.doi.org/10.1016/s0926-860x(03)00644-6.

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28

Jiang, Naimeng, Hua Sun, Dezhang Ren, Qi Pang, Fangming Jin, and Zhibao Huo. "A structure-activity controllable synthesis of skeletal CuAlZn catalyst for hydrogenation of bicarbonate to formic acid in water." Journal of CO2 Utilization 20 (July 2017): 218–23. http://dx.doi.org/10.1016/j.jcou.2017.05.015.

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29

Horváth, Henrietta, Gábor Laurenczy та Ágnes Kathó. "Water-soluble (η6-arene)ruthenium(II)-phosphine complexes and their catalytic activity in the hydrogenation of bicarbonate in aqueous solution". Journal of Organometallic Chemistry 689, № 6 (березень 2004): 1036–45. http://dx.doi.org/10.1016/j.jorganchem.2003.11.036.

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30

Bertini, Federica, Irene Mellone, Andrea Ienco, Maurizio Peruzzini, and Luca Gonsalvi. "Iron(II) Complexes of the Linearrac-Tetraphos-1 Ligand as Efficient Homogeneous Catalysts for Sodium Bicarbonate Hydrogenation and Formic Acid Dehydrogenation." ACS Catalysis 5, no. 2 (January 27, 2015): 1254–65. http://dx.doi.org/10.1021/cs501998t.

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31

Kathó, A. "Water-soluble analogs of [RuCl3(NO)(PPh3)2] and their catalytic activity in the hydrogenation of carbon dioxide and bicarbonate in aqueous solution." Journal of Molecular Catalysis A: Chemical 204-205 (September 15, 2003): 143–48. http://dx.doi.org/10.1016/s1381-1169(03)00293-0.

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32

Himeda, Yuichiro, Nobuko Onozawa-Komatsuzaki, Hideki Sugihara, Hironori Arakawa, and Kazuyuki Kasuga. "Half-Sandwich Complexes with 4,7-Dihydroxy-1,10-phenanthroline: Water-Soluble, Highly Efficient Catalysts for Hydrogenation of Bicarbonate Attributable to the Generation of an Oxyanion on the Catalyst Ligand." Organometallics 23, no. 7 (March 2004): 1480–83. http://dx.doi.org/10.1021/om030382s.

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33

Treigerman, Ziv, and Yoel Sasson. "Separation of Formate Ion from a Catalytic Mixture after a Hydrogenation Process of Bicarbonate Ion and Generation of Formic Acid—The Last Stage of the Formic Acid Cycle." American Journal of Analytical Chemistry 10, no. 08 (2019): 296–315. http://dx.doi.org/10.4236/ajac.2019.108022.

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34

Diercks, Justus Sebastian, Juan Herranz, Maximilian Georgi, Nataša Diklić, Piyush Chauhan, Adam Hugh Clark, Maarten Nachtegaal, Alexander Eychmüller, and Thomas J. Schmidt. "Interplay between Surface-Adsorbed CO and Bulk Pd-Hydride at CO2 Electroreduction Conditions." ECS Meeting Abstracts MA2022-01, no. 49 (July 7, 2022): 2095. http://dx.doi.org/10.1149/ma2022-01492095mtgabs.

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Анотація:
Due to its potential to replace fossil fuels in chemical processes by converting carbon dioxide (CO2) to industrial base reactants, the electroreduction of CO2 is receiving tremendous attention. Among the large number of electrocatalysts currently under investigation for this reaction, palladium (Pd) is increasingly appealing due to its ability to produce both carbon monoxide (CO) and formate at high selectivities depending on the applied potential. This unique change in selectivity between CO and formate at high vs. low overpotentials (i.e., -0.5 to -1.0 vs. -0.1 to -0.4 V vs. the reversible hydrogen electrode (VRHE), respectively) has been described multiple times on different Pd-electrocatalysts [1-3]. Those mechanistic investigations mainly focused on understanding the ability of palladium to form hydride (PdHx) under CO2 electroreduction conditions. While β-PdH is usually found at high overpotentials, the formation of α-PdH is described at low overpotentials, and a mixed-phase between both compositions is generally reported at intermediate overpotentials [1,3-5]. As a result, the CO2 reduction reaction (CO2RR) is assumed to take place on β-PdH at the high overpotentials leading to CO production, while α-PdH or a mixed α/β-phase is believed to be the active phase at low overpotentials associated with high formate yields [1,3,4]. However, large differences between the potential of β-PdH formation, as well as the extent of the mixed hydride state (i.e., featured as a sudden transition between α- and β-phases [3,4], or extending over hundreds of millivolts [1,5]), have been reported. In parallel to this, Pd-surface poisoning with CO is known to influence palladium’s CO2RR selectivity [2,3] while also slowing down hydride formation [6]. However, the precise interplay between surface-adsorbed CO and the formation of PdH, along with their combined effects on the mechanism of CO2 electroreduction remains poorly understood. In light of this, in this work, we investigated these effects using an unsupported Pd-aerogel with a web thickness of ≈ 6 nm, synthesized via a novel ethanolic synthesis approach [7]. We first analyzed the influence of the electrolyte composition (i.e., presence vs. absence of CO2 and bicarbonate) on the formation of surface-adsorbed CO and PdH by performing potential holds followed by positive linear sweep voltammograms in a rotating disk electrode (RDE) setup. As shown in Fig. 1A, these voltammograms featured two oxidation peaks at ≈ 0.8 vs. ≈ 1.0 VRHE that we could assign to the desorption of absorbed hydrogen and the oxidation of adsorbed CO, respectively. This in turn allowed us to track the formation of both of these species in relation to the applied potential and duration of the potential holds. Under CO2 electroreduction conditions, a full monolayer of CO was found to form across the entire CO2 electroreduction potential range. Moreover, large differences in the rate of PdH formation as a function of the applied potential were found in the presence of CO2 and/or bicarbonate, while in CO2- and bicarbonate-free electrolytes hydride formation is quasi-instantaneous at all potentials relevant for CO2 electroreduction. Time-dependent RDE investigations at constant potentials also revealed an initial decrease in the hydride content of the PdH phase during the formation of the CO monolayer, hinting at the involvement of this hydride in a hydrogenation step previously described as part of the CO2 electroreduction mechanism at low overpotentials [2]. Finally, these experiments were complemented with time-resolved in-situ X-ray absorption measurements that confirmed the formation of full β-PdH at all applied overpotentials under CO2 electroreduction conditions (see Fig. 1B), however, differences in the time-dependence of PdH formation on the applied potential were revealed. In summary, this contribution showcases the potential- and time-dependent CO monolayer formation under CO2RR conditions and its influence on PdH-formation. Specifically, our results reveal the independence of the final PdH-stoichiometry on the applied potential, while exposing the effect of the latter variable on the rates of CO-monolayer and β-PdH formation. On this basis, the mechanisms of CO2 electroreduction on Pd that have been proposed so far should be revisited to consider the simultaneous presence of full β-PdH and a near-full monolayer of CO at all overpotentials unveiled by our results. References: [1] D. Gao et al., Nano Res. 2017, 10 (6), 2181-2191. [2] X. Min et al., J. Am. Chem. Soc. 2015, 137 (14), 4701-8. [3] W. Zhu et al., Adv. Energy Mater. 2019, 9 (9), 1802840. [4] W. Sheng et al., Energy Environ. Sci. 2017, 10 (5), 1180-1185. [5] J.H. Lee et al., Chem. Commun. 2020, 56 (1), 106-108. [6] B. Łosiewicz et al., J. Electroanal. Chem. 2007, 611 (1-2), 26-34. [7] M. Georgi et al., Mater. Chem. Front. 2019, 3 (8), 1586-1592. Figure 1
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35

Zhu, Fengxiang, Ling Zhu-Ge, Guangfu Yang, and Shaolin Zhou. "Iron-Catalyzed Hydrogenation of Bicarbonates and Carbon Dioxide to Formates." ChemSusChem 8, no. 4 (January 21, 2015): 609–12. http://dx.doi.org/10.1002/cssc.201403234.

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36

Dai, Zengjin, Qi Luo, Hengjiang Cong, Jing Zhang, and Tianyou Peng. "New Ru(ii) N′NN′-type pincer complexes: synthesis, characterization and the catalytic hydrogenation of CO2 or bicarbonates to formate salts." New Journal of Chemistry 41, no. 8 (2017): 3055–60. http://dx.doi.org/10.1039/c6nj03855g.

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Анотація:
A new homogeneous system based on new Ru(ii)-N′NN′ pincer complexes has been successfully applied to the hydrogenation of CO2 to the formate, and complex 4 exhibits the best catalytic efficiency.
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37

Bulushev, Dmitri A., and Julian R. H. Ross. "Heterogeneous catalysts for hydrogenation of CO2 and bicarbonates to formic acid and formates." Catalysis Reviews 60, no. 4 (June 2018): 566–93. http://dx.doi.org/10.1080/01614940.2018.1476806.

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38

Federsel, Christopher, Carolin Ziebart, Ralf Jackstell, Wolfgang Baumann, and Matthias Beller. "Catalytic Hydrogenation of Carbon Dioxide and Bicarbonates with a Well-Defined Cobalt Dihydrogen Complex." Chemistry - A European Journal 18, no. 1 (December 6, 2011): 72–75. http://dx.doi.org/10.1002/chem.201101343.

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39

Šmidrkal, J., V. Ilko, V. Filip, M. Doležal, Z. Zelinková, J. Kyselka, I. Hrádková, and J. Velíšek. "Formation of acylglycerol chloro derivatives in vegetable oils and mitigation strategy." Czech Journal of Food Sciences 29, No. 4 (August 10, 2011): 448–56. http://dx.doi.org/10.17221/212/2011-cjfs.

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Анотація:
The most important acylglycerol chloroderivatives identified in foods are 3-chlorpropane-1,2-diol fatty acid esters (3-CPD esters) that are accompanied by epoxypropanol fatty acid esters formed in processed foods and, particularly, during the deodorisation of vegetable oils. Their content in refined vegetable oils is influenced by the oil composition, refining process conditions and process conditions of hydrogenation. Described and discussed here are the main pathways that lead to the formation of acylglycerols chloroderivatives and epoxypropanol fatty acid esters. The article offers detailed explanation of the reaction mechanisms using the well-known chemical principals based on experimental data. The conditions suitable for removing the unwanted products from the refined vegetable oils were studied in models containing variable proportions of agents (bicarbonates or carbonates) causing the decomposition of 3-CPD fatty acid esters.
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40

Gowrisankar, Saravanan, Christopher Federsel, Helfried Neumann, Carolin Ziebart, Ralf Jackstell, Anke Spannenberg, and Matthias Beller. "Synthesis of Stable Phosphomide Ligands and their Use in Ru-Catalyzed Hydrogenations of Bicarbonate and Related Substrates." ChemSusChem 6, no. 1 (December 28, 2012): 85–91. http://dx.doi.org/10.1002/cssc.201200732.

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41

Hamonnet, Johan, Michael Bennington, Sally Brooker, Vladimir Golovko, and Aaron Timothy Marshall. "Pyrolysed Co-N4 Macrocycles on Carbon Supports for the Efficient Electroreduction of CO2." ECS Meeting Abstracts MA2022-01, no. 14 (July 7, 2022): 959. http://dx.doi.org/10.1149/ma2022-0114959mtgabs.

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Анотація:
Converting CO2 into materials such as chemicals or synfuels is an attractive way to mitigate greenhouse gas emissions while producing value-added products1-4. Even though the intrinsic chemical stability of CO2 significantly limits its reactivity, the use of electrocatalysts allows its efficient reduction in a mild environment and at relatively low overpotentials5,6. Cobalt phthalocyanine (CoPC), cobalt tetra-phenyl porphyrin (CoTPP) and Vitamin B12 (VB12) are well-defined Co-N4 macrocycles whose incorporation into heterogeneous catalyst setups have led to materials with outstanding CO2 electroreduction reaction (CO2ERR) properties, most notably in the selective formation of CO at high current densities7-11. These Co-N4 macrocycles have also been used to manufacture catalysts efficient for the oxygen reduction reaction (ORR). Notably, the pyrolysis of the macrocyclic precursor supported by carbon materials allowed the fabrication of heterogeneous ORR catalysts with high loadings of catalytically active components, controlled local environments and enhanced stabilities12,13. While these properties could lead to these materials also being efficient catalysts for CO2ERR, to the best of our knowledge, such pyrolyzed catalysts have not been investigated for the CO2 reduction reaction. In this work, we report materials based on CoPC, CoTPP and VB12, supported by carbon black and pyrolyzed under argon, as efficient catalysts for the CO2ERR. The catalytic precursors were dispersed on carbon powders with ball-milling before being annealed at different temperatures chosen from the positions of the significant steps and plateaus observed by thermogravimetric analysis of the pure precursors. The structures of the resulting materials were analyzed by powder X-ray diffraction and X-ray absorption spectroscopy. The electrochemical behaviour of these materials for the CO2ERR were characterized in CO2-saturated potassium bicarbonate (KHCO3) electrolyte using a custom-made flow cell at a range of potentials, and the products of the reaction were analyzed with gas chromatography, 1H NMR spectroscopy and high-performance liquid chromatography. The high reactivity of the catalysts for the reduction of CO2 into CO was maintained for all materials treated at temperatures as high as 700 °C, even though the structures of their active sites were drastically different from that of the precursor molecules. The pyrolyzed materials also exhibited a change in correlation between the CO current densities and the KHCO3 concentration of the electrolyte, indicating that the reaction mechanism had changed compared to that of the pristine materials. 1 Peter, S. C. Reduction of CO2 to Chemicals and Fuels: A Solution to Global Warming and Energy Crisis. ACS Energy Letters 3, 1557-1561, doi:10.1021/acsenergylett.8b00878 (2018). 2 Lee, Z. H., Sethupathi, S., Lee, K. T., Bhatia, S. & Mohamed, A. R. An overview on global warming in Southeast Asia: CO2 emission status, efforts done, and barriers. Renewable and Sustainable Energy Reviews 28, 71-81, doi:10.1016/j.rser.2013.07.055 (2013). 3 Saeidi, S., Amin, N. A. S. & Rahimpour, M. R. Hydrogenation of CO2 to value-added products - A review and potential future developments. Journal of CO2 Utilization 5, 66-81, doi:10.1016/j.jcou.2013.12.005 (2014). 4 Zhao, G., Huang, X., Wang, X. X. & Wang, X. X. Progress in catalyst exploration for heterogeneous CO2 reduction and utilization: A critical review. Journal of Materials Chemistry A 5, 21625-21649, doi:10.1039/c7ta07290b (2017). 5 Finn, C., Schnittger, S., Yellowlees, L. J. & Love, J. B. Molecular approaches to the electrochemical reduction of carbon dioxide. Chemical Communications 48, 1392-1399, doi:10.1039/c1cc15393e (2012). 6 Torbensen, K., Boudy, B., Joulié, D., von Wolff, N. & Robert, M. Emergence of CO2 electrolyzers including supported molecular catalysts. Current Opinion in Electrochemistry 24, 49-55, doi:10.1016/j.coelec.2020.07.001 (2020). 7 Wang, M. et al. CO2 electrochemical catalytic reduction with a highly active cobalt phthalocyanine. Nature Communications 10, doi:10.1038/s41467-019-11542-w (2019). 8 Ni, W. et al. Dual single-cobalt atom-based carbon electrocatalysts for efficient CO2-to-syngas conversion with industrial current densities. Applied Catalysis B: Environmental 291, doi:10.1016/j.apcatb.2021.120092 (2021). 9 Jia, C. et al. Vitamin B12 on Graphene for Highly Efficient CO2 Electroreduction. ACS Appl Mater Interfaces 12, 41288-41293, doi:10.1021/acsami.0c10125 (2020). 10 Hu, B. et al. How does the ligands structure surrounding metal-N4 of Co-based macrocyclic compounds affect electrochemical reduction of CO2 performance? Electrochimica Acta 331, 135283, doi:10.1016/j.electacta.2019.135283 (2020). 11 Hu, X. M., Ronne, M. H., Pedersen, S. U., Skrydstrup, T. & Daasbjerg, K. Enhanced Catalytic Activity of Cobalt Porphyrin in CO2 Electroreduction upon Immobilization on Carbon Materials. Angew Chem Int Ed Engl 56, 6468-6472, doi:10.1002/anie.201701104 (2017). 12 Wan, G. et al. Tuning the Performance of Single-Atom Electrocatalysts: Support-Induced Structural Reconstruction. Chemistry of Materials 30, 7494-7502, doi:10.1021/acs.chemmater.8b02315 (2018). 13 Wan, G. et al. Anion-Regulated Selective Generation of Cobalt Sites in Carbon: Toward Superior Bifunctional Electrocatalysis. Adv Mater 29, doi:10.1002/adma.201703436 (2017).
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Fu, Xin-Pu, Laurent Peres, Jérôme Esvan, Catherine Amiens, Karine Philippot, and Ning Yan. "An air-stable, reusable Ni@Ni(OH)2 nanocatalyst for CO2/bicarbonate hydrogenation to formate." Nanoscale, 2021. http://dx.doi.org/10.1039/d1nr01054a.

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Анотація:
A novel foam-like Ni@Ni(OH)2 composite nanomaterial, synthesized by an organometallic approach, exhibited remarkable robustness and high catalytic performance for CO2 hydrogenation to formate.
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Rebreyend, Christophe, Evgeny A. Pidko, and Georgy A. Filonenko. "Homogeneous hydrogenation of saturated bicarbonate slurry to formates using multiphase catalysis." Green Chemistry, 2021. http://dx.doi.org/10.1039/d1gc02246f.

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Анотація:
Formic acid and formate salts are key intermediates along the pathways for CO2 utilization and hydrogen storage. Herein we report a highly efficient multiphase catalytic system utilizing ruthenium PNP pincer...
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"Palladium catalyzed hydrogenation of aqueous bicarbonate salts in formic acid production." Applied Catalysis A: General 121, no. 1 (January 1995): N3—N5. http://dx.doi.org/10.1016/0926-860x(95)85019-8.

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