Enzyme-catalyzed Sequential Reduction of Carbon Dioxide to Formaldehyde

doi:10.1016/j.cjche.2014.09.026

Abstract

Abstract: It has been reported that enzymatic-catalyzed reduction of CO₂ is feasible.Most of literature focuses on the conversion of CO₂ to methanol.Hereinwe put emphasis on the sequential conversion of CO₂ to formaldehyde and its single reactions. It appears that CO₂ pressure plays a critical role and higher pressure is greatly helpful to form more HCOOH as well as HCHO. The reverse reaction became severe in the reduction of CO₂ to formaldehyde after 10 h, decreasing HCHO production. Increasing the mass ratio of formate dehydrogenase to formaldehyde dehydrogenase could promote the sequential reaction. At concentrations of nicotinamide adenine dinucleotide lower than 100 mmol·L^-1, the reduction of CO₂ was accelerated by increasing cofactor concentration. The optimum pH value and concentration of phosphate buffer were determined as 6.0 and 0.05 mol·L^-1, respectively, for the overall reaction. It seems that thermodynamic factor such as pH is restrictive to the sequential reaction due to distinct divergence in appropriate pH range between its single reactions.

Key words: Carbon dioxide, Formic acid, Formaldehyde, Enzymatic-catalyzed, Sequential reduction

摘要： It has been reported that enzymatic-catalyzed reduction of CO₂ is feasible.Most of literature focuses on the conversion of CO₂ to methanol.Hereinwe put emphasis on the sequential conversion of CO₂ to formaldehyde and its single reactions. It appears that CO₂ pressure plays a critical role and higher pressure is greatly helpful to form more HCOOH as well as HCHO. The reverse reaction became severe in the reduction of CO₂ to formaldehyde after 10 h, decreasing HCHO production. Increasing the mass ratio of formate dehydrogenase to formaldehyde dehydrogenase could promote the sequential reaction. At concentrations of nicotinamide adenine dinucleotide lower than 100 mmol·L^-1, the reduction of CO₂ was accelerated by increasing cofactor concentration. The optimum pH value and concentration of phosphate buffer were determined as 6.0 and 0.05 mol·L^-1, respectively, for the overall reaction. It seems that thermodynamic factor such as pH is restrictive to the sequential reaction due to distinct divergence in appropriate pH range between its single reactions.

关键词: Carbon dioxide, Formic acid, Formaldehyde, Enzymatic-catalyzed, Sequential reduction

Wenfang Liu, Yanhui Hou, Benxiang Hou, Zhiping Zhao. Enzyme-catalyzed Sequential Reduction of Carbon Dioxide to Formaldehyde[J]. , 2014, 22(11/12): 1328-1332.

References

[1] H. Chen, S. Wang, M. Xiao, Y. Lu, Y. Meng, Direct synthesis of dimethyl carbonate from CO₂ and CH₂OH using 0.4 nm molecular sieve supported Cu-Ni bimetal catalyst, Chin. J. Chem. Eng. 20 (5) (2012) 906-913.
[2] M. Wang, Y. She, X. Zhou, H. Ji, Efficient solvent-free synthesis of chloropropene carbonate from the coupling reaction of CO₂ and epichlorohydrin catalyzed by magnesium porphyrins as chlorophyll-like catalysts, Chin. J. Chem. Eng. 19 (3) (2011) 446-451.
[3] K.Motokura, D. Kashiwame, A.Miyaji, T. Baba, Copper-catalyzed formic acid synthesis from CO₂ with hydrosilanes and H₂O, Org. Lett. 14 (10) (2012) 2642-2645.
[4] B.A. Parkinson, P.F.Weaver, Photoelectrochemical pumping of enzymatic CO₂ reduction, Nature 309 (5964) (1984) 148-149.
[5] Y.M. Yu, Y.P. Zhang, J.H. Fei, X.M. Zheng, Silica immobilized ruthenium catalyst for formic acid synthesis from supercritical carbon dioxide hydrogenation II: effect of reaction conditions on the catalyst performance, Chin. J. Chem. 23 (8) (2005) 977-982.
[6] A.V. Lobanov, S.N. Kholuiskaya, G.G. Komissarov, Photocatalytic synthesis of formaldehyde from CO₂ and H₂O₂, Dokl. Phys. Chem. 399 (1-3) (2004) 266-268.
[7] D.K. Lee, D.S. Kim, S.W. Kim, Selective formation of formaldehyde from carbon dioxide and hydrogen over PtCu/SiO₂, Appl. Organomet. Chem. 15 (2) (2001) 148-150.
[8] L.X. Zhang, Y.C. Zhang, S.Y. Chen, Effect of promoter SiO₂, TiO₂ or SiO₂-TiO₂ on the performance of CuO-ZnO-Al₂O₃ catalyst for methanol synthesis from CO₂ hydrogenation, Appl. Catal. A 415 (2012) 118-123.
[9] S.W. Park, O.S. Joo, K.D. Jung, H. Kim, S.H. Han, Development of ZnO/Al₂O₃ catalyst for reverse-water-gas-shift reaction of CAMERE (carbon dioxide hydrogenation to form methanol via a reverse-water-gas-shift reaction) process, Appl. Catal. A 211 (1) (2001) 81-90.
[10] A. Beuls, C. Swalus, M. Jacquemin, G. Heyen, A. Karelovic, P. Ruiz, Methanation of CO₂: further insight into the mechanism over Rh/gamma-Al₂O₃ catalyst, Appl. Catal. B 113 (2012) 2-10.
[11] D. Theleritis, S. Souentie, A. Siokou, A. Katsaounis, C.G. Vayenas, Hydrogenation of CO₂ over Ru/YSZ electropromoted catalysts, ACS Catal. 2 (5) (2012) 770-780.
[12] J. Qu, X. Zhang, Y. Wang, C. Xie, Electrochemical reduction of CO₂ on RuO₂/TiO₂ nanotubes composite modified Pt electrode, Electrochim. Acta 50 (16-17) (2005) 3576-3580.
[13] J.P. Popic,M.L. Avramov-Ivic, N.B. Vukovic, Reduction of carbon dioxide on ruthenium oxide and modified ruthenium oxide electrodes in 0.5MNaHCO₃, J. Electroanal. Chem. 421 (1-2) (1997) 105-110.
[14] M. Subrahmanyam, S. Kaneco, N. Alonso-Vante, A screening for the photo reduction of carbon dioxide supported on metal oxide catalysts for C1-C3 selectivity, Appl. Catal. B 23 (2-3) (1999) 169-174.
[15] D. Mandler, I.Willner, Photochemical fixation of carbon dioxide: enzymic photosynthesis of malic, aspartic, isocitric, and formic acids in artificial media, J. Chem. Soc. Perkin Trans. 2 (6) (1988) 997-1003.
[16] S. Kuwabata, R. Tsuda, H. Yoneyama, Electrochemical conversion of carbon dioxide to methanol with the assistance of formate dehydrogenase and methanol dehydrogenase as biocatalysts, J. Am. Chem. Soc. 116 (12) (1994) 5437-5443.
[17] R. Obert, B.C. Dave, Enzymatic conversion of carbon dioxide to methanol: enhanced methanol production in silica sol-gel matrices, J. Am. Chem. Soc. 121 (51) (1999) 12192-12193.
[18] Z.Y. Jiang, H. Wu, S.W. Xu, S.F. Huang, Q. Xie, Preliminary study on enzymatic conversion of carbon dioxide to methanol by sol-gel encapsulation, Chin. J. Catal. 23 (2) (2002) 162-164.
[19] Q. Sun, Y. Jiang, Z. Jiang, L. Zhang, X. Sun, J. Li, Green and efficient conversion of CO₂ to methanol by biomimetic coimmobilization of three dehydrogenases in protamine-templated titania, Ind. Eng. Chem. Res. 48 (9) (2009) 4210-4215.
[20] B. El-Zahab, D. Donnelly, P. Wang, Particle-tethered NADH for production of methanol from CO₂ catalyzed by coimmobilized enzymes, Biotechnol. Bioeng. 99 (3) (2008) 508-514.
[21] F. Baskaya, X. Zhao, M. Flickinger, P.Wang, Thermodynamic feasibility of enzymatic reduction of carbon dioxide to methanol, Appl. Biochem. Biotechnol. 162 (2) (2010) 391-398.
[22] P.K. Addo, R.L. Arechederra, A. Waheed, J.D. Shoemaker, W.S. Sly, S.D. Minteer, Methanol production via bioelectrocatalytic reduction of carbon dioxide: role of carbonic anhydrase in improving electrode performance, Electrochem. Solid-State Lett. 14 (4) (2011) E9-E13.
[23] Y. Lu, Z.Y. Jiang, S.W. Xu, H.Wu, Efficient conversion of CO₂ to formic acid by formate dehydrogenase immobilized in a novel alginate-silica hybrid gel, Catal. Today 115 (1-4) (2006) 263-268.
[24] M. Yoshimoto, T. Yamashita, T. Yamashiro, Stability and reactivity of liposomeencapsulated formate dehydrogenase and cofactor system in carbon dioxide gas-liquid flow, Biotechnol. Progr. 26 (4) (2010) 1047-1053.
[25] W.F. Liu, B.X. Hou, Y.H. Hou, Z.P. Zhao, Synthesis of formic acid from CO₂ catalyzed by formate dehydrogenase immobilized on hollow fiber membrane, Chin. J. Catal. 33 (4) (2012) 730-735.
[26] N. Wen, W.F. Liu, Y.H. Hou, Z.P. Zhao, The kinetics behavior of the reduction of formaldehyde catalyzed by alcohol dehydrogenase (ADH) and partial uncompetitive substrate inhibition by NADH, Appl. Biochem. Biotechnol. 170 (2013) 370-380.
[27] C.U. Galdiga, T. Greibrokk, Ultra trace determination of fluorinated aromatic carboxylic acids in aqueous reservoir fluids by solid phase extraction in combination with negative ion chemical ionisation mass spectrometry after derivatisation with pentafluorobenzyl bromide, Fresenius J. Anal. Chem. 361 (1998) 797-802.
[28] S. Uchiyama, E.Matsushima, S. Aoyagi,M. Ando, Simultaneous determination of C1-C4 carboxylic acids and aldehydes using 2,4-dinitrophenylhydrazine-impregnated silica gel and high-performance liquid chromatography, Anal. Chem. 76 (19) (2004) 5849-5854.