Abstract
Ammonia borane (NH3BH3) is a reducing agent, able to trap and convert carbon dioxide. In the present work, we used a reactive solid consisting of a mixture of 90 wt.% of NH3BH3 and 10 wt.% of palladium chloride, because the mixture reacts in a fast and exothermic way while releasing H2 and generating catalytic Pd0. We took advantage of such reactivity to trap and convert CO2 (7 bar), knowing besides that Pd0 is a CO2 hydrogenation catalyst. The operation (i.e. stage 1) was effective: BNH polymers, and B—O, C=O, C—O, and C—H bonds (like in BOCH3 and BOOCH groups) were identified. We then (in stage 2) pyrolyzed the as-obtained solid at 1250 °C and washed it with water. In doing so, we isolated cyclotriboric acid H3B3O6 (stemming from B2O3 formed at 1250 °C), hexagonal boron nitride, and graphitic carbon. In conclusion, the stage 1 showed that CO2 can be ‘trapped’ and converted, resulting in the formation of BOCH3 and BOOCH groups (possible sources of methanol and formic acid), and the stage 2 showed that CO2 transforms into graphitic carbon.
Similar content being viewed by others
References
Bonneuil C, Choquet P L, Franta B. Early warnings and emerging accountability: total’s responses to global warming, 1971–2021. Global Environmental Change, 2021, 71: 102386
Krishnan J N U, Jakka S C B. Carbon dioxide: no longer a global menace: a future source for chemicals. Materials Today: Proceedings, 2022, 58: 812–822
Zoelle A, McIlvried H. Enthalpy and free energy of CO2 utilization pathways. National Energy Technology Laboratory; Released April 26, 2017; reference DOE/NETL-2017/1849. Available at https://netl.doe.gov/projects/files/EnthalpyandFreeEnergyofCO2UtilizationPathways_042617.pdf (accessed November 9, 2021)
Franz D, Jandl C, Stark C, et al. Catalytic CO2 reduction with boron- and aluminum hydrides. ChemCatChem, 2019, 11(21): 5275–5281
Ra E C, Kim K Y, Kim E H, et al. Recycling carbon dioxide through catalytic hydrogenation: recent key developments and perspectives. ACS Catalysis, 2020, 10(19): 11318–11345
Boutin E, Robert M. Molecular electrochemical reduction of CO2 beyond two electrons. Trends in Chemistry, 2021, 3(5): 359–372
Variar A G, Ramyashree M S, Ail V U, et al. Influence of various operational parameters in enhancing photocatalytic reduction efficiency of carbon dioxide in a photoreactor: a review. Journal of Industrial and Engineering Chemistry, 2021, 99: 19–47
Kumaravel V, Bartlett J, Pillai S C. Photoelectrochemical conversion of carbon dioxide (CO2) into fuels and value-added products. ACS Energy Letters, 2020, 5(2): 486–519
Burr J G Jr, Brown W G, Heller H E. The reduction of carbon dioxide to formic acid. Journal of the American Chemical Society, 1950, 72(6): 2560–2562
Wartik T, Pearson R K. Reactions of carbon dioxide with sodium and lithium borohydrides. Journal of Inorganic and Nuclear Chemistry, 1958, 7(4): 404–411
Knopf I, Cummins C C. Revisiting CO2 reduction with NaBH4 under aprotic conditions: synthesis and characterization of sodium triformatoborohydride. Organometallics, 2015, 34(9): 1601–1603
Dovgaliuk I, Hagemann H, Leyssens T, et al. CO2-promoted hydrolysis of KBH4 for efficient hydrogen co-generation. International Journal of Hydrogen Energy, 2014, 39(34): 19603–19608
Fletcher C, Jiang Y, Amal R. Production of formic acid from CO2 reduction by means of potassium borohydride at ambient conditions. Chemical Engineering Science, 2015, 137: 301–307
Zhao Y, Zhang Z, Qian X, et al. Properties of carbon dioxide absorption and reduction by sodium borohydride under atmospheric pressure. Fuel, 2015, 142: 1–8
Grice K A, Groenenboom M C, Manuel J D A, et al. Examining the selectivity of borohydride for carbon dioxide and bicarbonate reduction in protic conditions. Fuel, 2015, 150: 139–145
Zhu W, Zhao J, Wang L, et al. Mechanochemical reactions of alkali borohydride with CO2 under ambient temperature. Journal of Solid State Chemistry, 2019, 277: 828–832
Picasso C V, Safin D A, Dovgaliuk I, et al. Reduction of CO2 with KBH4 in solvent-free conditions. International Journal of Hydrogen Energy, 2016, 41(32): 14377–14386
Kadota K, Sivaniah E, Horike S. Reactivity of borohydride incorporated in coordination polymers toward carbon dioxide. Chemical Communications, 2020, 56(38): 5111–5114
Lombardo L, Yang H, Zhao K, et al. Solvent- and catalyst-free carbon dioxide trap and reduction to formate with borohydride ionic liquid. ChemSusChem, 2020, 13(8): 2025–2031
Lombardo L, Ko Y, Zhao K, et al. Direct CO2 capture and reduction to high-end chemicals with tetraalkylammonium borohydrides. Angewandte Chemie International Edition in English, 2021, 60(17): 9580–9589
Ménard G, Stephan D W. Room temperature reduction of CO2 to methanol by Al-based frustrated Lewis pairs and ammonia borane. Journal of the American Chemical Society, 2010, 132(6): 1796–1797
Roy L, Zimmerman P M, Paul A. Changing lanes from concerted to stepwise hydrogenation: the reduction mechanism of frustrated Lewis acid-base pair trapped CO2 to methanol by ammonia-borane. Chemistry: A European Journal, 2011, 17(2): 435–439
Zeng G, Maeda S, Taketsugu T, et al. Catalytic hydrogenation of carbon dioxide with ammonia-borane by pincer-type phosphorus compounds: theoretical prediction. Journal of the American Chemical Society, 2016, 138(41): 13481–13484
Kumar A, Eyyathiyil J, Choudhury J. Reduction of carbon dioxide with ammonia-borane under ambient conditions: maneuvering a catalytic way. Inorganic Chemistry, 2021, 60(15): 11684–11692
Zhao T, Li C, Hu X, et al. Base-assisted transfer hydrogenation of CO2 to formate with ammonia borane in water under mild conditions. International Journal of Hydrogen Energy, 2021, 46(29): 15716–15723
Zhang J, Zhao Y, Akins D L, et al. CO2-enhanced thermolytic H2 release from ammonia borane. The Journal of Physical Chemistry C, 2011, 115(16): 8386–8392
Xiong R, Zhang J, Zhao Y, et al. Rapid release of 1.5 equivalents of hydrogen from CO2-treated ammonia borane. International Journal of Hydrogen Energy, 2012, 37(4): 3344–3349
Zhang J, Zhao Y, Guan X, et al. Formation of graphene oxide nanocomposites from carbon dioxide using ammonia borane. The Journal of Physical Chemistry C, 2012, 116(3): 2639–2644
Toche F, Chiriac R, Demirci U B, et al. Ammonia borane thermolytic decomposition in the presence of metal(II) chlorides. International Journal of Hydrogen Energy, 2012, 37(8): 6749–6755
Bahruji H, Bowker M, Hutchings G, et al. Pd/ZnO catalysts for direct CO2 hydrogenation to methanol. Journal of Catalysis, 2016, 343: 133–146
Petit J F, Dib E, Gaveau P, et al. 11B MAS NMR study of the thermolytic dehydrocoupling of two ammonia boranes upon the release of one equivalent of H2 at isothermal conditions. ChemistrySelect, 2017, 2(29): 9396–9401
Łodziana Z, Błoński P, Yan Y, et al. NMR chemical shifts of 11B in metal borohydrides from first-principle calculations. The Journal of Physical Chemistry C, 2014, 118(13): 6594–6603
Roy B, Pal U, Bishnoi A, et al. Exploring the homopolar dehydrocoupling of ammonia borane by solid-state multinuclear NMR spectroscopy. Chemical Communications, 2021, 57(15): 1887–1890
Bowden M, Autrey T, Brown I, et al. The thermal decomposition of ammonia borane: a potential hydrogen storage material. Current Applied Physics, 2008, 8(3–4): 498–500
NIST X-ray Photoelectron Spectroscopy (XPS) Database. Available at https://srdata.nist.gov/xps/ (accessed March 19, 2022)
Gouin X, Grange P, Bois L, et al. Characterization of the nitridation process of boric acid. Journal of Alloys and Compounds, 1995, 224(1): 22–28
Bachmann P, Düll F, Späth F, et al. A HR-XPS study of the formation of h-BN on Ni(1 1 1) from the two precursors, ammonia borane and borazine. The Journal of Chemical Physics, 2018, 149(16): 164709
Zhao J, Shi J, Zhang X, et al. A soft hydrogen storage material: poly(methyl acrylate)-confined ammonia borane with controllable dehydrogenation. Advanced Materials, 2010, 22(3): 394–397
Bresnehan M S, Hollander M J, Wetherington M, et al. Prospects of direct growth boron nitride films as substrates for graphene electronics. Journal of Materials Research, 2014, 29(3): 459–471
Qiao L, Li Q, Zhou Z, et al. Inert can be advantageous: advisable reconstruction and application of palladium chloride for the preferential oxidation of the hydrogen impurity in carbon monoxide streams. ChemCatChem, 2016, 8(11): 1909–1914
Mel’nikov N I, Peregood D P, Zhitnikov R A. Investigation of silver centres in glassy B2O3. Journal of Non-Crystalline Solids, 1974, 16(2): 195–205
Zhou F, Xu D, Shi M, et al. Investigation on microstructure and its transformation mechanisms of B2O3—SiO2—Al2O3—CaO brazing flux system. High-Temperature Materials and Processes, 2020, 39(1): 88–95
Chen L, Xu H F, He S J, et al. Thermal conductivity performance of polypropylene composites filled with polydopamine-functionalized hexagonal boron nitride. PLoS One, 2017, 12(1): e0170523
Lee E S, Park J K, Lee W S, et al. Effect of deposition temperature on cubic boron nitride thin film deposited by unbalanced magnetron sputtering method with a nanocrystalline diamond buffer layer. Metals and Materials International, 2013, 19(6): 1323–1326
Rao L S, Rao P V, Sharma M V N V D, et al. J-O parameters versus photoluminescence characteristics of 40Li2O—4MO (MO = Nb2O5, MoO3 and WO3)—55B2O3:1Nd2O3 glass systems. Optik, 2017, 142: 674–681
Krishnan K. The Raman spectra of boric acid. Proceedings of the Indian Academy of Sciences Section A: Physical Sciences, 1963, 57(2): 103–108
Yamauchi S, Doi S. Raman spectroscopic study on the behavior of boric acid in wood. Journal of Wood Science, 2003, 49(3): 227–234
Tuinstra F, Koenig J L. Raman spectrum of graphite. The Journal of Chemical Physics, 1970, 53(3): 1126–1130
Arenal R, Ferrari A C, Reich S, et al. Raman spectroscopy of single-wall boron nitride nanotubes. Nano Letters, 2006, 6(8): 1812–1816
Tatykaev B B, Burkitbayev M M, Uralbekov B M, et al. Mechanochemical synthesis of silver chloride nanoparticles by a dilution method in the system NH4Cl—AgNO3—NH4NO3. Acta Physica Polonica A, 2014, 126(4): 1044–1048
Kalidindi S B, Sanyal U, Jagirdar B R. Metal nanoparticles via the atom-economy green approach. Inorganic Chemistry, 2010, 49(9): 3965–3967
Chen W, Yu H, Wu G, et al. Ammonium aminodiboranate: a long-sought isomer of diammoniate of diborane and ammonia borane dimer. Chemistry: A European Journal, 2016, 22(23): 7727–7729
Acknowledgements
This work was supported by TUBITAK (Project No. 218M181) and CAMPUS FRANCE PHC BOSPHORUS (Project No. 42161TB). C.A.C.M. and U.B.D. want to acknowledge the CONACyT (Mexican National Council for Science and Technology) for the scholarship of C.A.C.M. (2017–2021).
Author information
Authors and Affiliations
Corresponding author
Supplementary Materials
Rights and permissions
About this article
Cite this article
Castilla-Martinez, C.A., Coşkuner Fılız, B., Petit, E. et al. Ammonia borane-based reactive mixture for trapping and converting carbon dioxide. Front. Mater. Sci. 16, 220610 (2022). https://doi.org/10.1007/s11706-022-0610-z
Received:
Accepted:
Published:
DOI: https://doi.org/10.1007/s11706-022-0610-z