Abstract
The oxygen evolution reaction (OER), which is based on the geometric structure and interfacial site tailoring of catalysts, is a good technique for producing hydrogen via water electrolysis. Here, we present fluorine and sulfur co-doped cobalt oxide nanosheets (SFO-Co) generated using a quick thermal exfoliation technique as efficient and long-lasting OER electrocatalysts. The SFO-Co catalyst has an ultralow overpotential of 170 mV at 10 mA cm−2 and a large double-layer capacitance (Cdl) of 94.9 mF cm−2, thanks to the synergistic effect of numerous anions, high density of active sites, and increased charge transfer capabilities. During a 50-h chronoamperometry test in 1 M KOH solution, the catalyst retains good performance at a steady current of 10 mA cm−2. This research not only reveals a low-cost, high-efficiency OER electrocatalyst, but it also offers a strategic design for multi-component electrocatalytic material systems that takes electronic reconfiguration into account.
Graphical abstract
Schematic illustration of two-dimensional sulfur and fluorine co-doped cobalt oxide nanosheets (SFO-Co)
Similar content being viewed by others
References
Meng FL, Zhong HX, Bao D, Yan JM, Zhang XB (2016) In situ coupling of strung Co4N and intertwined N-C fibers toward free-standing bifunctional cathode for robust, efficient, and flexible Zn air-batteries. J Am Chem Soc 138:10226–10231
Dang C, Mu Q, **e X, Sun X, Yang X, Zhang Y, Maganti S, Huang M, Jiang Q, Seok I, Du W, Hou C (2022) Recent progress in cathode catalyst for nonaqueous lithium oxygen batteries: a review. Adv Compos Hybrid Mater 5:1–21
Gao K, Wang B, Tao L, Cunning BV, Zhang Z, Wang S, Ruoff RS, Qu L (2019) Efficient metal-free electrocatalysts from N-doped carbon nanomaterials: mono-do** and Co-do**. Adv Mater 31:1805121
Hou C, Wang B, Murugadoss V, Vupputuri S, Chao Y, Guo Z, Wang C, Du W (2020) Recent advances in Co3O4 as anode materials for high-performance lithium-ion batteries. Eng Sci 11:19–30
Zhang JT, Zhao ZH, **a ZH, Dai LM (2015) A metal-free bifunctional electrocatalyst for oxygen reduction and oxygen evolution reactions. Nat Nanotechnol 10:444–452
Wang HF, Tang C, Li BQ, Zhang Q (2018) A review of anion regulated multi-anion transition metal compounds for oxygen evolution electrocatalysis. Inorg Chem Front 5:521–534
Bi MH, Hao YN, Zhang JM, Lei M, Bi K (2017) Particle size effect of BaTiO3 nanofillers on the energy storage performance of polymer nanocomposites. Nanoscale 9:16386–16395
Huang K, Zhang L, Xu T, Wei HH, Zhang RY, Zhang XY, Ge BH, Lei M, Ma J-Y, Liu L-M, Wu H (2019) 60 °C solution synthesis of atomically dispersed cobalt electrocatalyst with superior performance. Nat Commun 10:606
Culebras M, Collins GA, Beaucamp A, Geaney H, Collins MN (2022) Lignin/Si hybrid carbon nanofibers towards highly efficient sustainable Li-ion anode materials. Eng Sci 17:195–203
Li BQ, Zhang SY, Tang C, Cui X, Zhang Q (2017) Anionic regulated NiFe (oxy) sulfide electrocatalysts for water oxidation. Small 13:1700610
Huang K, Wang RY, Zhao SJ, Du P, Wang H, Wei HH, Long YZ, Deng BH, Lei M, Ge BH, Gou HY, Zhang R, Wu H (2020) Atomic species derived CoOx clusters on nitrogen doped mesoporous carbon as advanced bifunctional electro-catalysts for Zn-air battery. Energy Storage Mater 29:156–162
Hu XP, Wu H, Liu S, Gong S, Du Y, Li XL, Lu X, Qu JP (2022) Fabrication of organic shape-stabilized phase change material and its energy storage applications. Eng Sci 17:1–27
Yan ZQ, Sun ZH, Li AR, Liu HS, Guo ZH, Qian L (2021) Three-dimensional porous flower-like S-doped Fe2O3 for superior lithium storage. Adv Compos Hybrid Mater 4:716–724
Ishihara T, Yokoe K, Miyano T, Kusaba H (2019) Mesoporous MnCo2O4 spinel oxide for a highly active and stable air electrode for Zn-air rechargeable battery. Electrochim Acta 300:455–460
Yang CY, Li WY, Yu WT, Liu ML, Zhang YJ, Ma GL, Lei M, Liu WJ (2018) Amplification, resha**, fission and annihilation of optical solitons in dispersion-decreasing fiber. Nonlinear Dyn 92:203–213
Bai J, Mei J, Liao T, Sun Q, Chen ZG, Sun Z (2022) Molybdenum-promoted surface reconstruction in polymorphic cobalt for initiating rapid oxygen evolution. Adv Energy Mater 12:2103247
Budiyanto E, Salamon S, Wang Y, Wende H, Tüysüz H (2022) Phase segregation in cobalt iron oxide nanowires toward enhanced oxygen evolution reaction activity. JACS Au 2:697–710
Pei X, Zhang Y, Mu Y, Cui M, Tian F, Meng C (2022) Cobalt oxide decorated three-dimensional amorphous carbon/cobalt silicate composite derived from bamboo leaves enables the enhanced oxygen evolution reaction. Chem Eng Sci 251:117490
Xue Y, Fang J, Wang X, Xu Z, Zhang Y, Lv Q, Liu M, Zhu W, Zhuang Z (2021) Sulfate-functionalized RuFeOx as highly efficient oxygen evolution reaction electrocatalyst in acid. Adv Funct Mater 31:2101405
Su J, Ge R, Jiang K, Dong Y, Hao F, Tian Z, Chen G, Chen L (2018) Assembling ultrasmall copper-doped ruthenium oxide nanocrystals into hollow porous polyhedra: highly robust electrocatalysts for oxygen evolution in acidic media. Adv Mater 30:1801351
Zhao ZL, Wang HX, Feng Q, Gu S, Zhang Z, Xu H, Zeng L, Gu M, Li H (2020) Boosting the oxygen evolution reaction using defect-rich ultra-thin ruthenium oxide nanosheets in acidic media. Energ Environ Sci 13:5143–5151
Li G, Tang Y, Fu T, **ang Y, **ong Z, Si Y, Guo C, Jiang Z (2022) S, N co-doped carbon nanotubes coupled with CoFe nanoparticles as an efficient bifunctional ORR/OER electrocatalyst for rechargeable Zn-air batteries. Chem Eng J 429:132174
Ma Y, **e X, Yang W, Yu Z, Sun X, Zhang Y, Yang X, Kimura H, Hou C, Guo Z, Du W (2021) Recent advances in transition metal oxides with different dimensions as electrodes for high-performance supercapacitors. Adv Compos Hybrid Mater 4:906–924
Zhai Y, Yang W, **e X, Sun X, Wang J, Yang X, Naik N, Kimura H, Du W, Guo Z, Hou C (2022) Co3O4 nanoparticle-dotted hierarchical-assembled carbon nanosheet framework catalysts with the formation/decomposition mechanisms of Li2O2 for smart lithium-oxygen batteries. Inorg Chem Front 9:1115–1124
Li X, Yan J, Zhu KG (2021) Fabrication and characterization of Pt doped Ti/Sb-SnO2 electrode and its efficient electro-catalytic activity toward phenol. Eng Sci 15:38–46
Huang K, Xu YY, Song YP, Wang RY, Wei HH, Long YZ, Lei M, Tang HL, Guo JG, Wu H (2021) NiPS3 quantum sheets modified nitrogen-doped mesoporous carbon with boosted bifunctional oxygen electrocatalytic performance. J Mater Sci Technol 65:1–6
Singh AK, Ji S, Singh B, Das C, Choi H, Menezes PW, Indra A (2022) Alkaline oxygen evolution: exploring synergy between fcc and hcp cobalt nanoparticles entrapped in N-doped graphene. Mater Today Chem 23:100668
Zheng H, Ma F, Yang H, Wu X, Wang R, Jia D, Wang Z, Lu N, Ran F, Peng S (2022) Mn, N co-doped Co nanoparticles/porous carbon as air cathode for highly efficient rechargeable Zn-air batteries. Nano Res 15:1942–1948
Reier T, Oezaslan M, Strasser P (2012) Electrocatalytic oxygen evolution reaction (OER) on Ru, Ir, and Pt catalysts: a comparative study of nanoparticles and bulk materials. ACS Catal 2:1765
Huang K, Wang RY, Wu HB, Wang H, He X, Wei HH, Wang SP, Zhang R, Lei M, Guo W, Ge BH, Wu H (2019) Direct immobilization of an atomically dispersed Pt catalyst by suppressing heterogeneous nucleation at -40 °C. J Mater Chem A 7:25779–25784
Lin Y, Zhang ML, Zhao LX, Wang LM, Cao DL, Gong YQ (2021) Ru doped bimetallic phosphide derived from 2D metal organic framework as active and robust electrocatalyst for water splitting. Appl Surf Sci 536:147952
Huang K, Guo S, Wang RY, Lin S, Hussain N, Wei HH, Deng BH, Long YZ, Lei M, Tang HL, Wu H (2020) Two-dimensional MOF/MOF derivative arrays on nickel foam as efficient bifunctional coupled oxygen electrodes. Chinese J Catal 41:1754–1760
**g C, Zhang Y, Zheng J, Ge S, Lin J, Pan D, Naik N, Guo Z (2022) In-situ constructing visible light CdS/Cd-MOF photocatalyst with enhanced photodegradation of methylene blue. Particuology 69:111–122
Gao S, Zhao X, Fu Q, Zhang T, Zhu J, Hou F, Ni J, Zhu C, Li T, Wang Y, Murugadoss V, Mersal GAM, Ibrahim MM, El-Bahy ZM, Huang M, Guo Z (2022) Highly transmitted silver nanowires-SWCNTs conductive flexible film by nested density structure and aluminum-doped zinc oxide cap** layer for flexible amorphous silicon solar cells. J Mater Sci Technol 126:152–160
Yu Z, Yan Z, Zhang F, Wang J, Shao Q, Murugadoss V, Alhadhrami A, Mersal GAM, Ibrahim MM, El-Bahy ZM, Li Y, Huang M, Guo Z (2022) Waterborne acrylic resin co-modified by itaconic acid and γ-methacryloxypropyl triisopropoxidesilane for improved mechanical properties, thermal stability, and corrosion resistance. Prog Org Coat 168:106875
Shui J, Wang M, Du F, Dai L (2015) N-doped carbon nanomaterials are durable catalysts for oxygen reduction reaction in acidic fuel cells. Sci Adv 1:e1400129
Gong K, Feng D, Zhenhai X, Michael D, Liming D (2009) Nitrogen-doped carbon nanotube arrays with high electrocatalytic activity for oxygen reduction. Science 323:760–764
**e W, Huang J, Huang L, Geng S, Song S, Tsiakaras P, Wang Y (2022) Novel fluorine-doped cobalt molybdate nanosheets with enriched oxygen-vacancies for improved oxygen evolution reaction activity. Appl Catal B 303:120871
Shamloofard M, Shahrokhian S (2021) Dual-electrocatalysis behavior of star-like zinc-cobalt-sulfide decorated with cobalt-molybdenum-phosphide in hydrogen and oxygen evolution reactions. Nanoscale 13:17576–17591
Li M, Liu H, Feng L (2021) Fluoridation-induced high-performance catalysts for the oxygen evolution reaction: a mini review. Electrochem Commun 122:106901
Liu Z, Huang Y-C, Wang Y, Cen J, Yang H, Chen X, Tong X, Su D, Dong C-L, Wang S (2019) Quinary defect-rich ultrathin bimetal hydroxide nanosheets for water oxidation. ACS Appl Mater Interfaces 11:44018–44025
Li R, Wang H, Hu F, Chan KC, Liu X, Lu Z, Wang J, Li Z, Zeng L, Li Y, Wu X, **ong Y (2021) IrW nanochannel support enabling ultrastable electrocatalytic oxygen evolution at 2 A cm(-2) in acidic media. Nat Commun 12:3540
Du HY, Ren XJ, Pan D, An YL, Wei YH, Liu XD, Hou LF, Liu BS, Liu MM, Guo ZH (2021) Effect of phosphating solution pH value on the formation of phosphate conversion coatings for corrosion behaviors on AZ91D. Adv Compos Hybrid Mater 4:401–414
Omeir MY, Wadi VS, Alhassan SM (2020) Inverse vulcanized sulfure-cycloalkene copolymers: effect of ring size and unsaturation on thermal properties. Mater Lett 259:126887
Bi K, Guo YS, Liu XM, Zhao Q, **ao JH, Lei M, Zhou J (2014) Magnetically tunable Mie resonance-based dielectric metamaterials. Sci Rep 4:7001
Dou YH, Liao T, Ma ZQ, Tian DL, Liu QN, **ao F, Sun ZQ, Kim JH, Dou SX (2016) Graphene-like holey Co3O4 nanosheets as a highly efficient catalyst for oxygen evolution reaction. Nano Energy 30:267–275
Kim M, Kim S, Song D, Oh S, Chang KJ, Cho E (2018) Promotion of electrochemical oxygen evolution reaction by chemical coupling of cobalt to molybdenum carbide. Appl Catal B 227:340–348
Wu N, Zhao B, Liu J, Li Y, Chen Y, Chen L, Wang M, Guo Z (2021) MOF-derived porous hollow Ni/C composites with optimized impedance matching as lightweight microwave absorption materials. Adv Compos Hybrid Mater 4:707–715
Chen P, Zhou T, Wang S, Zhang N, Tong Y, Ju H, Chu W, Wu C, **e Y (2018) Dynamic migration of surface fluorine anions on cobalt-based materials to achieve enhanced oxygen evolution catalysis. Angew Chem Int Ed 57:15471–15475
Li X, Niu Z, Jiang J, Ai L (2016) Cobalt nanoparticles embedded in porous N-rich carbon as an efficient bifunctional electrocatalyst for water splitting. J Mater Chem A 4:3204–3209
Lin H, Liu N, Shi Z, Guo Y, Tang Y, Gao Q (2016) Cobalt-do** in molybdenum-carbide nanowires toward efficient electrocatalytic hydrogen evolution. Adv Functional Mater 26:5590–5598
Liu PF, Yang S, Zhang B, Yang HG (2016) Defect-rich ultrathin cobalt-iron layered double hydroxide for electrochemical overall water splitting. ACS Appl Mater Interfaces 8:34474–34481
Cai P, Huang J, Chen J, Wen Z (2017) Oxygen-containing amorphous cobalt sulfide porous nanocubes as high-activity electrocatalysts for the oxygen evolution reaction in an alkaline/neutral medium. Angew Chem Int Ed 129:4936–4939
Detsi E, Cook JB, Lesel BK, Turner CL, Liang Y-L, Robbennolt S, Tolbert SH (2016) Mesoporous Ni60Fe30Mn10-alloy based metal/metal oxide composite thick films as highly active and robust oxygen evolution catalysts. Energy Environ Sci 9:540–549
McCrory CCL, Jung S, Peters JC, Jaramillo TF (2013) Benchmarking heterogeneous electrocatalysts for the oxygen evolution reaction. J Am Chem Soc 135:16977–16987
Wu D, Chen D, Zhu J, Mu S (2021) Ultralow Ru incorporated amorphous cobalt-based oxides for high-current-density overall water splitting in alkaline and seawater media. Small 17:2102777
Luo Y, Wu Y, Wu D, Huang C, **ao D, Chen H, Zheng S, Chu PK (2020) NiFe layered double hydroxide synchronously activated by heterojunctions and vacancies for the oxygen evolution reaction. ACS Appl Mater Interfaces 12:42850–42858
Li X, Hao X, Wang Z, Abudula A, Guan G (2017) In-situ intercalation of NiFe LDH materials: an efficient approach to improve electrocatalytic activity and stability for water splitting. J Power Sources 347:193–200
Long X (2015) Co intake mediated formation of ultrathin nanosheets of transition metal LDHdan advanced electrocatalyst for oxygen evolution reaction. Chem Commun 51:1120–1123
Li Z, Cai L, Song M, Chen YC, Wang X, Li J, Wang J, Wang P, Tian L (2020) Ternary FeCoNi alloy nanoparticles embedded in N-doped carbon nanotubes for efficient oxygen evolution reaction electrocatalysis. Electrochim Acta 339:135886
Zhan ZM, Liang XL, Li JF, Qian JM, Liu YG, Yang SL, Wang Y, Gao DQ, Xue DS (2020) Interfacial engineering of NiO/NiCo2O4 porous nanofibers as efficient bifunctional catalysts for rechargeable zinc-air batteries. ACS Appl Mater Interfaces 12:21661–21669
Huang C, Ouyang T, Zou Y, Li N, Liu ZQ (2018) Ultrathin NiCo2Px nanosheets strongly coupled with CNTs as efficient and robust electrocatalysts for overall water splitting. J Mater Chem A 6:7420–7427
Gu Y, Chen S, Ren J, Jia YA, Chen CM, Komarneni S, Yang DJ, Yao XD (2018) Electronic structure tuning in Ni3FeN/r-GO aerogel toward bifunctional electrocatalyst for overall water splitting. ACS Nano 12:245–253
Xue ZQ, Li X, Li QL, Cai MK, Liu K, Liu M, Ke ZF, Liu XL, Li GQ (2019) Interfacial electronic structure modulation of NiTe nanoarrays with NiS nanodots facilitates electrocatalytic oxygen evolution. Adv Mater 31:1900430
Cao X, Johnson E, Nath M (2019) Identifying high-efficiency oxygen evolution electrocatalysts from Co-Ni-Cu based selenides through combinatorial electrodeposition. J Mater Chem A 7:9877–9889
Nsanzimana JMV, Peng YC, Xu YY, Thia L, Wang C, **a BY, Wang X (2018) An efficient and earth-abundant oxygen-evolving electrocatalyst based on amorphous metal borides. Adv Energy Mater 8:1701475
Zhang H, Li H, Akram B, Wang X (2019) Fabrication of NiFe layered double hydroxide with well-defined laminar superstructure as highly efficient oxygen evolution electrocatalysts. Nano Res 12:1327–1331
Tian T, Zheng M, Lin J, Meng X, Ding Y (2019) Amorphous Ni-Fe double hydroxide hollow nanocubes enriched with oxygen vacancies as efficient electrocatalytic water oxidation catalysts. Chem Commun 55:1044–1047
Cui X, Ren P, Deng D, Deng J, Bao X (2016) Single layer graphene encapsulating non-precious metals as high-performance electrocatalysts for water oxidation. Energy Environ Sci 9:123–129
Wang C, Yang H, Zhang Y, Wang Q (2019) NiFe alloy nanoparticles with hcp crystal structure stimulate superior oxygen evolution reaction electrocatalytic activity. Angew Chem Int Ed 58:6099
Zhou Q, Chen Y, Zhao G, Lin Y, Yu Z, Xu X, Wang X, Liu HK, Sun W, Dou SX (2018) Active-site-enriched iron-doped nickel/cobalt hydroxide nanosheets for enhanced oxygen evolution reaction. Acs Catal 8:5382–5390
Esswein AJ, McMurdo MJ, Ross PN, Bell AT, Tilley TD (2009) Size-dependent activity of Co3O4 nanoparticle anodes for alkaline water electrolysis. J Phys Chem C 113:15068–15072
Waag F, Gökce B, Kalapu C, Bendt G, Salamon S, Landers J, Hagemann U, Heidelmann M, Schulz S, Wende H, Hartmann N, Behrens M, Barcikowski S (2017) Adjusting the catalytic properties of cobalt ferrite nanoparticles by pulsed laser fragmentation in water with defined energy dose. Sci rep 7:1–13
Deng X, Öztürk S, Weidenthaler C, Tüysüz H (2017) Iron-induced activation of ordered mesoporous nickel cobalt oxide electrocatalyst for the oxygen evolution reaction. ACS Appl Mater Interfaces 9:21225–21233
Song F, Hu X (2014) Exfoliation of layered double hydroxides for enhanced oxygen evolution catalysis. Nat Commun 5:4477
Zhong L, Bao Y, Yu X, Feng L (2019) An Fe-doped NiTe bulk crystal as a robust catalyst for the electrochemical oxygen evolution reaction. Chem Commun 55:9347–9350
Zhu R, Ding J, Xu Y, Yang J, Xu Q, Pang H (2018) π-Conjugated molecule boosts metal-organic frameworks as efficient oxygen evolution reaction catalysts. Small 14:1803576
Yang N, Tang C, Wang K, Du G, Asiri AM, Sun X (2016) Iron-doped nickel disulfide nanoarray: a highly efficient and stable electrocatalyst for water splitting. Nano Res 9:3346–3354
Zhang Q, Yan D, Nie Z, Qiu X, Wang S, Yuan J, Su D, Wang G, Wu Z (2018) Iron-doped NiCoP porous nanosheet arrays as a highly efficient electrocatalyst for oxygen evolution reaction. ACS Appl Energy Mater 1:571–579
Wu Z, Zou Z, Huang J, Gao F (2018) Fe-doped NiO mesoporous nanosheets array for highly efficient overall water splitting. J Catal 358:243–252
Fan H, Yu H, Zhang Y, Zheng Y, Luo Y, Dai Z, Li B, Zong Y, Yan Q (2017) Fe-doped Ni3C nanodots in N-doped carbon nanosheets for efficient hydrogen-evolution and oxygen-evolution electrocatalysis. Angew Chem Int Ed 56:12566–12570
Cao C, Ma D-D, Xu Q, Wu XT, Zhu QL (2019) Semisacrificial template growth of self-supporting MOF nanocomposite electrode for efficient electrocatalytic water oxidation. Adv Functional Mater 29:1807418
Song F, Busch MM, Lassalle-Kaiser B, Hsu CS, Petkucheva E, Bensimon M, Chen HM, Corminboeuf C, Hu X (2019) An unconventional iron nickel catalyst for the oxygen evolution reaction. ACS Cent Sci 5:558–568
Lemoine K, Lhoste J, Hémon-Ribaud A, Heidary N, Maisonneuve V, Guiet A, Kornienko N (2019) Investigation of mixed-metal (oxy) fluorides as a new class of water oxidation electrocatalysts. Chem Sci 10:9209–9218
Han H, Woo J, Hong YR, Chung YC, Mhin S (2019) Polarized electronic configuration in transition metal-fluoride oxide hollow nanoprism for highly efficient and robust water splitting. ACS Appl Energy Mater 2:3999–4007
Liu Z, Liu H, Gu X, Feng L (2020) Oxygen evolution reaction efficiently catalyzed by a quasi-single-crystalline cobalt fluoride. Chem Eng J 397:125500
Funding
This study is supported financially by the Zhejiang Province Public Welfare Technology Application Research Project (Grant No. LGG22E010003), the Fundamental Research Funds for the Central Universities (2021XD-A04-2), the National Natural Science Foundations of China (Grant Nos. 61974011, 12074408), the Youth Innovation Promotion Association CAS (Grant No. E2VB021), and the Fund of State Key Laboratory of Information Photonics and Optical Communications (Bei**g University of Posts and Telecommunications, People’s Republic of China).
Author information
Authors and Affiliations
Contributions
ZB Zhao and Y Lin, data curation, investigation, methodology, roles/writing — original draft, and writing — review and editing. JB Wu, conceptualization, data curation, formal analysis, roles/writing — original draft, and writing — review and editing. J Li, methodology, funding acquisition, roles/writing — original draft, and writing — review and editing. M Lei, investigation, methodology, and validation. All authors read and approved the manuscript.
Corresponding authors
Ethics declarations
Conflict of interest
The authors declare no competing interests.
Additional information
Publisher's Note
Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Supplementary Information
Below is the link to the electronic supplementary material.
Rights and permissions
Springer Nature or its licensor holds exclusive rights to this article under a publishing agreement with the author(s) or other rightsholder(s); author self-archiving of the accepted manuscript version of this article is solely governed by the terms of such publishing agreement and applicable law.
About this article
Cite this article
Zhao, Z., Lin, Y., Wu, J. et al. Mixed-phase cobalt-based nanosheets prepared by rapid thermal annealing for oxygen evolution catalysis. Adv Compos Hybrid Mater 5, 2589–2600 (2022). https://doi.org/10.1007/s42114-022-00537-9
Received:
Revised:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s42114-022-00537-9