Skip to main content
SpringerLink
Log in

Crystal facet engineering of perovskite cobaltite with optimized electronic regulation for water splitting

晶面工程优化钴基钙钛矿电子结构及其电解水性能

  • Articles
  • Published:
Science China Materials Aims and scope Submit manuscript

Abstract

The correlation between crystal facets and electronic configurations of perovskite is closely related to the intrinsic activity for water splitting. Herein, we proposed a unique molten-salt method (MSM) to manipulate the electronic properties of LaCoO3 by fine-tuning its crystal facet and atomic doping. LaCoO3 samples with oriented (110) (LCO (110)) and (111) (LCO (111)) facets were motivated by a capping agent (Sr2+). Compared with the LCO (111) plane, the LCO (110) and Sr-doped LCO (111) (LSCO (111)) planes possessed higher O 2p positions, stronger Co 3d–O 2p covalencies, and higher Co spin states by inducing CoO6 distortion, thus leading to superior oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) performances. Specifically, the overpotentials at 10 mA cm−2 were 299, 322, and 289 mV for LCO (110), LCO (111), and LSCO (111), respectively. In addition, the (110) crystal facet and Sr substitution bestowed enhanced stability on LaCoO3 due to the strengthened Co–O bonding. The present work enlightens new avenues of regulating electronic properties by crystal facet engineering and atom doping and provides a valuable reference for the electron structure-electrocatalytic activity connection for OER and HER.

摘要

钴基钙钛矿催化剂的晶面和电子构型与其本征电解水活性密切相关. 本文中, 我们提出了一种独特的熔盐方法以调控LaCoO3的晶面类型和原子掺杂, 进而调制其电子结构. 通过引入封端剂(Sr2+), 我们制备了具有特定(110)晶面(LCO (110))和(111)晶面(LCO (111))的LaCoO3样品. 与LCO (111)相比, CoO6八面体的畸变使LCO (110)和LSCO (111)具有更高的O 2p位置、更强的Co 3d–O 2p共价性以及更高的Co自旋态,从而具有更优的析氧反应(OER)和析氢反应(HER)性能. 其中, LCO(110)、LCO (111)和LSCO (111)在10 mA cm−2处的过电位分别为299,322和289 mV. 此外, (110)晶面和Sr掺杂使Co–O键能增强, 进而提升了LaCoO3的稳定性. 本工作通过晶面工程和原子掺杂为电子结构的调控开辟了新的途径, 并为阐明OER和HER催化剂的电子结构-电催化活性关系提供了参考.

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

Similar content being viewed by others

References

  1. Song J, Wei C, Huang ZF, et al. A review on fundamentals for designing oxygen evolution electrocatalysts. Chem Soc Rev, 2020, 49: 2196–2214

    Article  CAS  Google Scholar 

  2. Ma P, Yang H, Luo Y, et al. Strongly coupled interface structure in CoFe/Co3O4 nanohybrids as efficient oxygen evolution reaction catalysts. ChemSusChem, 2019, 12: 4442–4451

    Article  CAS  Google Scholar 

  3. Cheng Z, Pi Y, Shao Q, et al. Boron-doped amorphous iridium oxide with ultrahigh mass activity for acidic oxygen evolution reaction. Sci China Mater, 2021, 64: 2958–2966

    Article  CAS  Google Scholar 

  4. Cui B, Liu C, Zhang J, et al. Waste to wealth: Defect-rich Ni-incorporated spent LiFePO4 for efficient oxygen evolution reaction. Sci China Mater, 2021, 64: 2710–2718

    Article  CAS  Google Scholar 

  5. Chen H, Shi L, Liang X, et al. Optimization of active sites via crystal phase, composition, and morphology for efficient low-iridium oxygen evolution catalysts. Angew Chem Int Ed, 2020, 59: 19654–19658

    Article  CAS  Google Scholar 

  6. Yang H, Long Y, Zhu Y, et al. Crystal lattice distortion in ultrathin Co(OH)2 nanosheets inducing elongated Co–OOH bonds for highly efficient oxygen evolution reaction. Green Chem, 2017, 19: 5809–5817

    Article  CAS  Google Scholar 

  7. Li Y, He J, Cheng W, et al. High mass-specific reactivity of a defect-enriched Ru electrocatalyst for hydrogen evolution in harsh alkaline and acidic media. Sci China Mater, 2021, 64: 2467–2476

    Article  CAS  Google Scholar 

  8. Wang Y, Liu S, Qin Q, et al. Praseodymium iridium oxide as a competitive electrocatalyst for oxygen evolution reaction in acid media. Sci China Mater, 2021, 64: 2193–2201

    Article  CAS  Google Scholar 

  9. Jiang B, Cheong WC, Tu R, et al. Regulating the electronic structure of NiFe layered double hydroxide/reduced graphene oxide by Mn incorporation for high-efficiency oxygen evolution reaction. Sci China Mater, 2021, 64: 2729–2738

    Article  CAS  Google Scholar 

  10. Zhou YN, Wang FL, Dou SY, et al. Motivating high-valence Nb doping by fast molten salt method for NiFe hydroxides toward efficient oxygen evolution reaction. Chem Eng J, 2022, 427: 131643

    Article  CAS  Google Scholar 

  11. Dong B, Xie JY, Wang N, et al. Zinc ion induced three-dimensional Co9S8 nano-neuron network for efficient hydrogen evolution. Renew Energy, 2020, 157: 415–423

    Article  CAS  Google Scholar 

  12. Wang H, Zhou M, Choudhury P, et al. Perovskite oxides as bifunctional oxygen electrocatalysts for oxygen evolution/reduction reactions—A mini review. Appl Mater Today, 2019, 16: 56–71

    Article  Google Scholar 

  13. Wang X, Huang K, Yuan L, et al. Molten salt flux synthesis, crystal facet design, characterization, electronic structure, and catalytic properties of perovskite cobaltite. ACS Appl Mater Interfaces, 2018, 10: 28219–28231

    Article  CAS  Google Scholar 

  14. Sun Y, Ren X, Sun S, et al. Engineering high-spin state cobalt cations in spinel zinc cobalt oxide for spin channel propagation and active site enhancement in water oxidation. Angew Chem Int Ed, 2021, 60: 14536–14544

    Article  CAS  Google Scholar 

  15. Wu H, Yang T, Du Y, et al. Identification of facet-governing reactivity in hematite for oxygen evolution. Adv Mater, 2018, 30: 1804341

    Article  CAS  Google Scholar 

  16. Fu W, Zhou X, Wang Y, et al. Crystal-plane-controlled restructuring and enhanced oxygen-involving performances of bifunctional catalyst. Appl Catal A-Gen, 2021, 628: 118417

    Article  CAS  Google Scholar 

  17. Harb M, Jeantelot G, Basset JM. Insights into the most suitable TiO2 surfaces for photocatalytic O2 and H2 evolution reactions from DFT calculations. J Phys Chem C, 2019, 123: 28210–28218

    Article  CAS  Google Scholar 

  18. Hwang J, Akkiraju K, Corchado-García J, et al. A perovskite electronic structure descriptor for electrochemical CO2 reduction and the competing H2 evolution reaction. J Phys Chem C, 2019, 123: 24469–24476

    Article  CAS  Google Scholar 

  19. Grimaud A, May KJ, Carlton CE, et al. Double perovskites as a family of highly active catalysts for oxygen evolution in alkaline solution. Nat Commun, 2013, 4: 2439

    Article  CAS  Google Scholar 

  20. Lu Z, Wang H, Kong D, et al. Electrochemical tuning of layered lithium transition metal oxides for improvement of oxygen evolution reaction. Nat Commun, 2014, 5: 4345

    Article  CAS  Google Scholar 

  21. Suntivich J, May KJ, Gasteiger HA, et al. A perovskite oxide optimized for oxygen evolution catalysis from molecular orbital principles. Science, 2011, 334: 1383–1385

    Article  CAS  Google Scholar 

  22. Zhou Y, Du Y, Xi S, et al. Spinel manganese ferrites for oxygen electrocatalysis: Effect of Mn valency and occupation site. Electrocatalysis, 2018, 9: 287–292

    Article  CAS  Google Scholar 

  23. Zhou Y, Sun S, Song J, et al. Enlarged Co–O covalency in octahedral sites leading to highly efficient spinel oxides for oxygen evolution reaction. Adv Mater, 2018, 30: 1802912

    Article  CAS  Google Scholar 

  24. Zeng J, Zheng Y, Rycenga M, et al. Controlling the shapes of silver nanocrystals with different capping agents. J Am Chem Soc, 2010, 132: 8552–8553

    Article  CAS  Google Scholar 

  25. Wang D, Jiang H, Zong X, et al. Crystal facet dependence of water oxidation on BiVO4 sheets under visible light irradiation. Chem Eur J, 2011, 17: 1275–1282

    Article  CAS  Google Scholar 

  26. Liu G, Yu JC, Lu GQM, et al. Crystal facet engineering of semiconductor photocatalysts: Motivations, advances and unique properties. Chem Commun, 2011, 47: 6763–6783

    Article  CAS  Google Scholar 

  27. Tong Y, Guo Y, Chen P, et al. Spin-state regulation of perovskite cobaltite to realize enhanced oxygen evolution activity. Chem, 2017, 3: 812–821

    Article  CAS  Google Scholar 

  28. Mefford JT, Rong X, Abakumov AM, et al. Water electrolysis on La1−xSrxCoO3−δ perovskite electrocatalysts. Nat Commun, 2016, 7: 11053

    Article  CAS  Google Scholar 

  29. Grimaud A, Diaz-Morales O, Han B, et al. Activating lattice oxygen redox reactions in metal oxides to catalyse oxygen evolution. Nat Chem, 2017, 9: 457–465

    Article  CAS  Google Scholar 

  30. Read MSD, Islam MS, Watson GW, et al. Defect chemistry and surface properties of LaCoO3. J Mater Chem, 2000, 10: 2298–2305

    Article  CAS  Google Scholar 

  31. Williams ED, Bartelt NC. Surface faceting and the equilibrium crystal shape. Ultramicroscopy, 1989, 31: 36–48

    Article  Google Scholar 

  32. Moll N, Kley A, Pehlke E, et al. GaAs equilibrium crystal shape from first principles. Phys Rev B, 1996, 54: 8844–8855

    Article  CAS  Google Scholar 

  33. Li X, Dai H, Deng J, et al. Au/3DOM LaCoO3: High-performance catalysts for the oxidation of carbon monoxide and toluene. Chem Eng J, 2013, 228: 965–975

    Article  CAS  Google Scholar 

  34. Chen CQ, Li W, Cao CY, et al. Enhanced catalytic activity of perovskite oxide nanofibers for combustion of methane in coal mine ventilation air. J Mater Chem, 2010, 20: 6968–6974

    Article  CAS  Google Scholar 

  35. Hong WT, Gadre M, Lee YL, et al. Tuning the spin state in LaCoO3 thin films for enhanced high-temperature oxygen electrocatalysis. J Phys Chem Lett, 2013, 4: 2493–2499

    Article  CAS  Google Scholar 

  36. May KJ, Carlton CE, Stoerzinger KA, et al. Influence of oxygen evolution during water oxidation on the surface of perovskite oxide catalysts. J Phys Chem Lett, 2012, 3: 3264–3270

    Article  CAS  Google Scholar 

  37. Rousseau S, Loridant S, Delichere P, et al. La(1−x)SrxCo1−yFcyO3 perovskites prepared by sol-gel method: Characterization and relationships with catalytic properties for total oxidation of toluene. Appl Catal B-Environ, 2009, 88: 438–447

    Article  CAS  Google Scholar 

  38. Yan X, Jia Y, Chen J, et al. Defective-activated-carbon-supported Mn−Co nanoparticles as a highly efficient electrocatalyst for oxygen reduction. Adv Mater, 2016, 28: 8771–8778

    Article  CAS  Google Scholar 

  39. Merino N, Barbero B, Grange P, et al. LaCaCoO perovskite-type oxides: Preparation, characterisation, stability, and catalytic potentiality for the total oxidation of propane. J Catal, 2005, 231: 232–244

    Article  CAS  Google Scholar 

  40. Kucharczyk B, Tylus W. Effect of Pd or Ag additive on the activity and stability of monolithic LaCoO3 perovskites for catalytic combustion of methane. Catal Today, 2004, 90: 121–126

    Article  CAS  Google Scholar 

  41. Zhang Z, Long J, Xie X, et al. Controlling the synergistic effect of oxygen vacancies and N dopants to enhance photocatalytic activity of N-doped TiO2 by H2 reduction. Appl Catal A-Gen, 2012, 425–426: 117–124

    Article  CAS  Google Scholar 

  42. Shukla R, Jain A, Miryala M, et al. Spin dynamics and unconventional magnetism in insulating La(1−2x)Sr2xCo(1−x)NbxO3. J Phys Chem C, 2019, 123: 22457–22469

    Article  CAS  Google Scholar 

  43. Choudhury B, Dey M, Choudhury A. Shallow and deep trap emission and luminescence quenching of TiO2 nanoparticles on Cu doping. Appl Nanosci, 2014, 4: 499–506

    Article  CAS  Google Scholar 

  44. Cheng XQ, Ma CY, Yi XY, et al. Structural, morphological, optical and photocatalytic properties of Gd-doped TiO2 films. Thin Solid Films, 2016, 615: 13–18

    Article  CAS  Google Scholar 

  45. Qin Q, Cai Q, Li J, et al. High quantum efficiency achieved on BiVO4 photoanode for efficient solar water oxidation. Sol RRL, 2019, 3: 1900301

    Article  CAS  Google Scholar 

  46. Xiao Z, Huang YC, Dong CL, et al. Operando identification of the dynamic behavior of oxygen vacancy-rich Co3O4 for oxygen evolution reaction. J Am Chem Soc, 2020, 142: 12087–12095

    Article  CAS  Google Scholar 

  47. Zou Z, Wang T, Zhao X, et al. Expediting in-situ electrochemical activation of two-dimensional metal-organic frameworks for enhanced OER intrinsic activity by iron incorporation. ACS Catal, 2019, 9: 7356–7364

    Article  CAS  Google Scholar 

  48. Zhang YM, Han RQ, Liu XD. Preparation and electrical properties of La1/2(1−x)Ba1/2COO3 cathode materials. Sci Tech Engrg, 2011, 35: 21–24

    CAS  Google Scholar 

  49. Li D, Zhang W, Zeng J, et al. Nickel-doped Co4N nanowire bundles as efficient electrocatalysts for oxygen evolution reaction. Sci China Mater, 2021, 64: 1889–1899

    Article  CAS  Google Scholar 

  50. Li L, Yang H, Miao J, et al. Unraveling oxygen evolution reaction on carbon-based electrocatalysts: Effect of oxygen doping on adsorption of oxygenated intermediates. ACS Energy Lett, 2017, 2: 294–300

    Article  CAS  Google Scholar 

  51. Chen Y, Bu Y, Zhang Y, et al. A highly efficient and robust nanofiber cathode for solid oxide fuel cells. Adv Energy Mater, 2017, 7: 1601890

    Article  CAS  Google Scholar 

  52. Zhang Y, Chen Y, Chen F. In-situ quantification of solid oxide fuel cell electrode microstructure by electrochemical impedance spectroscopy. J Power Sources, 2015, 277: 277–285

    Article  CAS  Google Scholar 

  53. Korotin MA, Ezhov SY, Solovyev IV, et al. Intermediate-spin state and properties of LaCoO3. Phys Rev B, 1996, 54: 5309–5316

    Article  CAS  Google Scholar 

Download references

Acknowledgements

This work was supported by the National Natural Science Foundation of China (52174283).

Author information

Authors and Affiliations

  1. State Key Laboratory of Heavy Oil Processing, College of Chemistry and Chemical Engineering, China University of Petroleum (East China), Qingdao, 266580, China

    Ya-Nan Zhou  (周亚楠), Feng-Ge Wang  (王凤格), Yi-Nuo Zhen  (甄依诺), Bin Dong  (董斌) & Yong-Ming Chai  (柴永明)

  2. CNOOC Tianjin Chemical Research and Design Institute Co., Ltd, Tianjin, 300131, China

    Jun Nan  (南军)

Authors
  1. Ya-Nan Zhou  (周亚楠)
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Feng-Ge Wang  (王凤格)
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Yi-Nuo Zhen  (甄依诺)
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Jun Nan  (南军)
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Bin Dong  (董斌)
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Yong-Ming Chai  (柴永明)
    View author publications

    You can also search for this author in PubMed Google Scholar

Contributions

Zhou YN conducted the experiment and wrote the paper; Wang FG and Zhen YN performed the characterization measurements. Nan J carried out some data analysis and proposed valuable suggestions. Dong B and Chai YM designed and supervised this study. All authors contributed to the general discussion.

Corresponding authors

Correspondence to Bin Dong  (董斌) or Yong-Ming Chai  (柴永明).

Additional information

Conflict of interest

The authors declare that they have no conflict of interest.

Supplementary information

Experimental details and supporting data are available in the online version of the paper.

Ya-Nan Zhou received her bachelor’s degree of engineering from Qingdao University of Science and Technology in 2019. She is pursuing her doctor degree under the supervision of Prof. Yong-Ming Chai and Bin Dong in the State Key Laboratory of Heavy Oil Processing, College of Chemistry and Chemical Engineering, China University of Petroleum (East China). Her primary research interests focus on electrochemical and photoelectrochemical water splitting.

Bin Dong received his PhD degree from Lanzhou University in 2008. He was doing research as a visiting scholar at Marquette University from 2014.03 to 2015.03. He is an associate professor at the College of Chemistry and Chemical Engineering, China University of Petroleum (East China). His research interests focus on the designing and synthesis of functional materials for energy conversion and storage inclduing electrocatalysts and photoelectrocatalysts for water splitting.

Yong-Ming Chai received his PhD degree from China University of Petroleum (East China) in 2008. Now he is a professor at the State Key Laboratory of Heavy Oil Processing, College of Chemistry and Chemical Engineering, China University of Petroleum (East China). He was doing research as a visiting scholar at Marquette University from 2015.03 to 2016.03. His research interests are the catalysts for the hydrodesulfurization process of heavy oil and transition metal-based electrocatalysts for green hydrogen.

Supplementary Material

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Zhou, YN., Wang, FG., Zhen, YN. et al. Crystal facet engineering of perovskite cobaltite with optimized electronic regulation for water splitting. Sci. China Mater. 65, 2665–2674 (2022). https://doi.org/10.1007/s40843-022-2016-5

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s40843-022-2016-5

Keywords

Search

Navigation