Skip to main content

Advertisement

SpringerLink
Log in

Notable hydrogen production on LaxCa1−xCoO3 perovskites via two-step thermochemical water splitting

  • Energy materials
  • Published:
Journal of Materials Science Aims and scope Submit manuscript

Abstract

High-performance thermochemical water splitting catalyst is the key in solar-driven H2 production for the development of sustainable and clean energy technology. Perovskite oxides have been considered promising redox catalysts for two-step thermochemical H2O splitting cycles due to their remarkable oxygen exchange capacity at low thermal heating temperatures. This study is the first to investigate perovskite series of La1−xCaxCoO3 for two-step thermochemical H2O splitting cycles. The Ca doping contents in La1−xCaxCoO3 perovskites showed a significant effect on the O2 and H2 production performances. Increasing the Ca doping content has greatly increased O2 evolution during the thermal reduction process. However, high Ca dopant content significantly weakened the reaction thermodynamics of the subsequent H2O splitting and led to lower re-oxidation yields. After tuning the Ca doping level from 0.2 to 0.8, La0.6Ca0.4CoO3 was identified as the best trade-off among the tested La1−xCaxCoO3 perovskites. The thermal reduction and water splitting temperatures were also systematically investigated to optimize the thermochemical operational conditions. La0.6Ca0.4CoO3 showed maximum H2 production of 587 µmol g−1 when the two-step thermochemical H2O splitting carried out between 1300 and 900 °C, eighteen times higher than that of CeO2 under the same experimental condition. More importantly, La0.6Ca0.4CoO3 also exhibited fairly good catalytic stability during the thermochemical cycling test and has strong potential for long-term applications.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Figure 1
Figure 2
Figure 3
Figure 4
Figure 5
Figure 6
Figure 7
Figure 8

Similar content being viewed by others

References

  1. Hosseini SE, Wahid MA (2016) Hydrogen production from renewable and sustainable energy resources: promising green energy carrier for clean development. Renew Sustain Energy Rev 57:850–866

    CAS  Google Scholar 

  2. Wen M, Cui Y, Kuwahara Y, Mori K, Yamashita H (2016) Non-noble-metal nanoparticle supported on metal–organic framework as an efficient and durable catalyst for promoting H2 production from ammonia borane under visible light irradiation. ACS Appl Mater Interfaces 8:21278–21284

    CAS  Google Scholar 

  3. Zhu L, Fan J (2015) Thermodynamic analysis of H2 production from CaO sorption-enhanced methane steam reforming thermally coupled with chemical looping combustion as a novel technology. Int J Renew Energy Res 39:356–369

    CAS  Google Scholar 

  4. Gil MV, Esteban-Díez G, Pevida C, Chen D, Rubiera F (2014) H2 production by steam reforming with in situ CO2 capture of biomass-derived bio-oil. Energy Procedia 63:6815–6823

    CAS  Google Scholar 

  5. Al-Mamun M, Wang Y, Liu P et al (2016) One-step solid phase synthesis of a highly efficient and robust cobalt pentlandite electrocatalyst for the oxygen evolution reaction. J Mater Chem A 4:18314–18321

    CAS  Google Scholar 

  6. Al-Mamun M, Su X, Zhang H et al (2016) Strongly coupled CoCr2O4/carbon nanosheets as high performance electrocatalysts for oxygen evolution reaction. Small 12:2866–2871

    CAS  Google Scholar 

  7. Al-Mamun M, Yin H, Liu P et al (2017) Carbon-encapsulated heazlewoodite nanoparticles as highly efficient and durable electrocatalysts for oxygen evolution reactions. Nano Res 10:3522–3533

    CAS  Google Scholar 

  8. Al-Mamun M, Zhu Z, Yin H et al (2016) The surface sulfur doping induced enhanced performance of cobalt catalysts in oxygen evolution reactions. Chem Commun 52:9450–9453

    CAS  Google Scholar 

  9. Ulloa OA, Huynh MT, Richers CP, Bertke JA, Nilges MJ, Hammes-Schiffer S, Rauchfuss TB (2016) Mechanism of H2 production by models for the [NiFe]-hydrogenases: role of reduced hydrides. J Am Chem Soc 138:9234–9245

    CAS  Google Scholar 

  10. Zhang J, Qi L, Ran J, Yu J, Qiao SZ (2014) Ternary NiS/ZnxCd1−xS/reduced graphene oxide nanocomposites for enhanced solar photocatalytic H2-production activity. Adv Energy Mater 4:1301925–1301930

    Google Scholar 

  11. Steinfeld A (2005) Solar thermochemical production of hydrogen: a review. Sol Energy 78:603–615

    CAS  Google Scholar 

  12. Loutzenhiser PG, Meier A, Steinfeld A (2010) Review of the two-step H2O/CO2-splitting solar thermochemical cycle based on Zn/ZnO redox reactions. Materials 3:4922–4938

    Google Scholar 

  13. Weibel D, Jovanovic ZR, Galvez E, Steinfeld A (2014) Mechanism of Zn particle oxidation by H2O and CO2 in the presence of ZnO. Chem Mater 26:6486–6495

    CAS  Google Scholar 

  14. Stamatiou A, Loutzenhiser PG, Steinfeld A (2010) Solar syngas production via H2O/CO2 splitting thermochemical cycles with Zn/ZnO and FeO/Fe3O4 redox reactions. Chem Mater 22:851–859

    CAS  Google Scholar 

  15. Leveque G, Abanades S (2015) Investigation of thermal and carbothermal reduction of volatile oxides (ZnO, SnO2, GeO2, and MgO) via solar-driven vacuum thermogravimetry for thermochemical production of solar fuels. Thermochim Acta 605:86–94

    CAS  Google Scholar 

  16. Leveque G, Abanades S (2013) Kinetic analysis of high-temperature solid–gas reactions by an inverse method applied to ZnO and SnO2 solar thermal dissociation. Chem Eng J 217:139–149

    CAS  Google Scholar 

  17. Gokon N, Mataga T, Kondo N, Kodama T (2011) Thermochemical two-step water splitting by internally circulating fluidized bed of NiFe2O4 particles: successive reaction of thermal-reduction and water-decomposition steps. Int J Hydrogen Energy 36:4757–4767

    CAS  Google Scholar 

  18. Kodama T, Gokon N, Yamamoto R (2008) Thermochemical two-step water splitting by ZrO2-supported NixFe3−xO4 for solar hydrogen production. Sol Energy 82:73–79

    CAS  Google Scholar 

  19. Miller JE, McDaniel AH, Allendorf MD (2014) Considerations in the design of materials for solar-driven fuel production using metal oxide thermochemical cycles. Adv Energy Mater 4:1300469–1300488

    Google Scholar 

  20. Roeb M, Neises M, Monnerie N et al (2012) Materials-related aspects of thermochemical water and carbon dioxide splitting: a review. Materials 5:2015–2054

    CAS  Google Scholar 

  21. Takacs M, Scheffe JR, Steinfeld A (2015) Oxygen nonstoichiometry and thermodynamic characterization of Zr doped ceria in the 1573–1773 K temperature range. Phys Chem Chem Phys 17:7813–7822

    CAS  Google Scholar 

  22. Scheffe JR, Welte M, Steinfeld A (2014) Thermal reduction of ceria within an aerosol reactor for H2O and CO2 splitting. Ind Eng Chem Res 53:2175–2182

    CAS  Google Scholar 

  23. Cooper T, Scheffe JR, Galvez ME, Jacot R, Patzke G, Steinfeld A (2015) Lanthanum manganite perovskites with Ca/Sr A-site and Al B-site doping as effective oxygen exchange materials for solar thermochemical fuel production. Energy Technol 3:1130–1142

    CAS  Google Scholar 

  24. Muhich CL, Ehrhart BD, Al-Shankiti I, Ward BJ, Musgrave CB, Weimer AW (2016) A review and perspective of efficient hydrogen generation via solar thermal water splitting. Wiley Interdiscip Rev Energy Environ 5:261–287

    CAS  Google Scholar 

  25. Tao S, Irvine JT (2003) A redox-stable efficient anode for solid-oxide fuel cells. Nat Mater 2:320–323

    CAS  Google Scholar 

  26. Petric A, Huang P, Tietz F (2000) Evaluation of La–Sr–Co–Fe–O perovskites for solid oxide fuel cells and gas separation membranes. Solid State Ion 135:719–725

    CAS  Google Scholar 

  27. Scheffe JR, Weibel D, Steinfeld A (2013) Lanthanum–strontium–manganese perovskites as redox materials for solar thermochemical splitting of H2O and CO2. Energy Fuels 27:4250–4257

    CAS  Google Scholar 

  28. Yang CK, Yamazaki Y, Aydin A, Haile SM (2014) Thermodynamic and kinetic assessments of strontium-doped lanthanum manganite perovskites for two-step thermochemical water splitting. J Mater Chem A 2:13612–13623

    CAS  Google Scholar 

  29. McDaniel AH, Miller EC, Arifin D et al (2013) Sr- and Mn-doped LaAlO3-delta for solar thermochemical H2 and CO production. Energy Environ Sci 6:2424–2428

    CAS  Google Scholar 

  30. McDaniel A, Ambrosini A, Coker E, Miller J, Chueh W, O’Hayre R, Tong J (2014) Nonstoichiometric perovskite oxides for solar thermochemical H2 and CO Production. Energy Procedia 49:2009–2018

    CAS  Google Scholar 

  31. Deml AM, Stevanović V, Holder AM, Sanders M, O’Hayre R, Musgrave CB (2014) Tunable oxygen vacancy formation energetics in the complex perovskite oxide SrxLa1−xMnyAl1−yO3. Chem Mater 26:6595–6602

    CAS  Google Scholar 

  32. Galvez ME, Jacot R, Scheffe J, Cooper T, Patzke G, Steinfeld A (2015) Physico-chemical changes in Ca, Sr and Al doped LaMnO perovskites upon thermochemical splitting of CO2 via redox cycling. Phys Chem Chem Phys 17:6629–6634

    CAS  Google Scholar 

  33. Dey S, Naidu BS, Govindaraj A, Rao CNR (2015) Noteworthy performance of La1−xCaxMnO3 perovskites in generating H2 and CO by the thermochemical splitting of H2O and CO2. Phys Chem Chem Phys 17:122–125

    CAS  Google Scholar 

  34. Bork AH, Kubicek M, Struzik M, Rupp JLM (2015) Perovskite La0.6Sr0.4Cr1−xCoxO3 solid solutions for solar-thermochemical fuel production: strategies to lower the operation temperature. J Mater Chem A 3:15546–15557

    CAS  Google Scholar 

  35. Dey S, Naidu BS, Rao CNR (2015) Ln0.5A0.5MnO3 (Ln = Lanthanide, A = Ca, Sr) perovskites exhibiting remarkable performance in the thermochemical generation of CO and H2 from CO2 and H2O. Chem Eur J 21:7077–7081

    CAS  Google Scholar 

  36. Dey S, Naidu BS, Rao CNR (2016) Beneficial effects of substituting trivalent ions in the B-site of La0.5Sr0.5Mn1−xAxO3 (A = Al, Ga, Sc) on the thermochemical generation of CO and H2 from CO2 and H2O. Dalton Trans 45:2430–2435

    CAS  Google Scholar 

  37. Gerasimov E, Kulikovskaya N, Chuvilin A, Isupova L, Tsybulya S (2016) Microstructural changes in La1−xCaxCoO3−δ solid solutions under the influence of catalytic reaction of methane combustion. Top Catal 59:1354–1360

    CAS  Google Scholar 

  38. Murai K-I, Nagai K, Takahashi M, Takakusa S, Moriga T (2015) Study of thermoelectric properties of Ca-doped LaCoO3. Mod Phys Lett B 29:1540026–1540030

    Google Scholar 

  39. Dueso C, Thompson C, Metcalfe I (2015) High-stability, high-capacity oxygen carriers: iron oxide-perovskite composite materials for hydrogen production by chemical looping. Appl Energy 157:382–390

    CAS  Google Scholar 

  40. Oumezzine M, Amaral J, Mompean F, Hernández MG, Oumezzine M (2016) Structural, magnetic, magneto-transport properties and Bean-Rodbell model simulation of disorder effects in Cr3+ substituted La0.67Ba0.33MnO3 nanocrystalline synthesized by modified Pechini method. RSC Adv 6:32193–32201

    CAS  Google Scholar 

  41. Wang L, Al-Mamun M, Zhong YL et al (2017) Ca2+ and Ga3+ doped LaMnO3 perovskite as a highly efficient and stable catalyst for two-step thermochemical water splitting. Sustain Energy Fuels 1:1013–1017

    CAS  Google Scholar 

  42. Wang L, Al-Mamun M, Liu P, Wang Y, Yang HG, Zhao H (2017) La1−xCaxMn1−yAlyO3 perovskites as efficient catalysts for two-step thermochemical water splitting in conjunction with exceptional hydrogen yields. Chin J Catal 38:1079–1086

    CAS  Google Scholar 

  43. Kumar DA, Selvasekarapandian S, Nithya H, Leiro J, Masuda Y, Kim S-D, Woo S-K (2013) Effect of calcium doping on LaCoO3 prepared by Pechini method. Powder Technol 235:140–147

    CAS  Google Scholar 

  44. Melo D, Vieira F, Costa T et al (2013) Lanthanum cobaltite black pigments with perovskite structure. Dyes Pigment 98:459–463

    CAS  Google Scholar 

  45. Zhu H, Zhang P, Dai S (2015) Recent advances of lanthanum-based perovskite oxides for catalysis. ACS Catal 5:6370–6385

    CAS  Google Scholar 

  46. Athayde DD, Souza DF, Silva AMA, Vasconcelos D, Nunes EHM, Diniz da Costa JC, Vasconcelos WL (2016) Review of perovskite ceramic synthesis and membrane preparation methods. Ceram Int 42:6555–6571

    CAS  Google Scholar 

  47. Demont A, Abanades S (2015) Solar thermochemical conversion of CO2 into fuel via two-step redox cycling of non-stoichiometric Mn-containing perovskite oxides. J Mater Chem A 3:3536–3546

    CAS  Google Scholar 

  48. Gokon N, Sagawa S, Kodama T (2013) Comparative study of activity of cerium oxide at thermal reduction temperatures of 1300–1550 °C for solar thermochemical two-step water-splitting cycle. Int J Hydrogen Energy 38:14402–14414

    CAS  Google Scholar 

Download references

Acknowledgements

This work was financially supported by the Australian Research Council (ARC) and the National Natural Science Foundation of China (Grant Nos. 51372248, 51432009).

Author information

Author notes

  1. Lulu Wang and Mohammad Al-Mamun have contributed equally to this work.

Authors and Affiliations

  1. Centre for Clean Environment and Energy, Gold Coast Campus, Griffith University, Southport, QLD, 4222, Australia

    Lulu Wang, Mohammad Al-Mamun, Porun Liu, Yun Wang & Huijun Zhao

  2. Key Laboratory for Ultrafine Materials of Ministry of Education, School of Materials Science and Engineering, East China University of Science and Technology, Shanghai, 200237, China

    Hua Gui Yang

  3. Centre for Environmental and Energy Nanomaterials, Institute of Solid State Physics, Chinese Academy of Sciences, Hefei, 230031, China

    Huijun Zhao

Authors
  1. Lulu Wang
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Mohammad Al-Mamun
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Porun Liu
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Yun Wang
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Hua Gui Yang
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Huijun Zhao
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Huijun Zhao.

Ethics declarations

Conflict of interest

The authors declare that they have no conflict of interest.

Electronic supplementary material

Below is the link to the electronic supplementary material.

Supplementary material 1 (DOCX 2305 kb)

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Wang, L., Al-Mamun, M., Liu, P. et al. Notable hydrogen production on LaxCa1−xCoO3 perovskites via two-step thermochemical water splitting. J Mater Sci 53, 6796–6806 (2018). https://doi.org/10.1007/s10853-018-2004-2

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s10853-018-2004-2

Search

Navigation