The semiconductor–electrolyte interface dominates the behaviours of semiconductor electrocatalysis, which has been modelled as a Schottky-analogue junction according to classical electron transfer theories. However, this model cannot be used to explain the extremely high carrier accumulations in ultrathin semiconductor catalysis observed in our work. Inspired by the recently developed ion-controlled electronics, we revisit the semiconductor–electrolyte interface and unravel a universal self-gating phenomenon through microcell-based in situ electronic/electrochemical measurements to clarify the electronic-conduction modulation of semiconductors during the electrocatalytic reaction. We then demonstrate that the type of semiconductor catalyst strongly correlates with their electrocatalysis; that is, n-type semiconductor catalysts favour cathodic reactions such as the hydrogen evolution reaction, p-type ones prefer anodic reactions such as the oxygen evolution reaction and bipolar ones tend to perform both anodic and cathodic reactions. Our study provides new insight into the electronic origin of the semiconductor–electrolyte interface during electrocatalysis, paving the way for designing high-performance semiconductor catalysts.
This is a preview of subscription content, access via your institution
Open Access articles citing this article.
Nature Communications Open Access 27 October 2023
Surface charge as activity descriptors for electrochemical CO2 reduction to multi-carbon products on organic-functionalised Cu
Nature Communications Open Access 20 January 2023
Nature Communications Open Access 22 December 2022
Access Nature and 54 other Nature Portfolio journals
Get Nature+, our best-value online-access subscription
$29.99 / 30 days
cancel any time
Subscribe to this journal
Receive 12 print issues and online access
$259.00 per year
only $21.58 per issue
Rent or buy this article
Prices vary by article type
Prices may be subject to local taxes which are calculated during checkout
The data that support the findings of this study are available from the corresponding author on reasonable request.
Allen, J. & Bard, L. R. F. Electrochemical Methods: Fundamentals and Applications 2nd edn (Wiley, 2000).
Memming, R. Semiconductor Electrochemistry 2nd edn (Wiley, 2015).
Rajeshwar, K. Fundamentals of Semiconductor Electrochemistry and Photoelectrochemistry Vol. 6 (Wiley, 2002).
Nozik, A. J. & Memming, R. Physical chemistry of semiconductor–liquid interfaces. J. Phys. Chem. 100, 13061–13078 (1996).
Gao, Y. Q., Georgievskii, Y. & Marcus, R. A. On the theory of electron transfer reactions at semiconductor electrode/liquid interfaces. J. Chem. Phys. 112, 3358–3369 (2000).
Lewis, N. S. Progress in understanding electron-transfer reactions at semiconductor/liquid interfaces. J. Phys. Chem. B 102, 4843–4855 (1998).
Fajardo, A. M. & Lewis, N. S. Rate constants for charge transfer across semiconductor–liquid interfaces. Science 274, 969–972 (1996).
Marcus, R. A. On the theory of oxidation–reduction reactions involving electron transfer. I. J. Chem. Phys. 24, 966–978 (1956).
Gerischer, H. Charge transfer processes at semiconductor–electrolyte interfaces in connection with problems of catalysis. Surf. Sci. 18, 97–122 (1969).
Bisri, S. Z., Shimizu, S., Nakano, M. & Iwasa, Y. Endeavor of iontronics: from fundamentals to applications of ion-controlled electronics. Adv. Mater. 29, 1607054 (2017).
Du, H., Lin, X., Xu, Z. & Chu, D. Electric double-layer transistors: a review of recent progress. J. Mater. Sci. 50, 5641–5673 (2015).
Wang, Y. et al. Structural phase transition in monolayer MoTe2 driven by electrostatic doping. Nature 550, 487–491 (2017).
Saito, Y., Kasahara, Y., Ye, J., Iwasa, Y. & Nojima, T. Metallic ground state in an ion-gated two-dimensional superconductor. Science 350, 409–413 (2015).
Vanmaekelbergh, D., Houtepen, A. J. & Kelly, J. J. Electrochemical gating: a method to tune and monitor the (opto)electronic properties of functional materials. Electrochim. Acta 53, 1140–1149 (2007).
Saito, Y. et al. Superconductivity protected by spin-valley locking in ion-gated MoS2. Nat. Phys. 12, 144–149 (2016).
Ye, J. T. et al. Liquid-gated interface superconductivity on an atomically flat film. Nat. Mater. 9, 125–128 (2010).
Liu, L. et al. Probing the crystal plane effect of Co3O4 for enhanced electrocatalytic performance toward efficient overall water splitting. ACS Appl. Mater. Interfaces 9, 27736–27744 (2017).
Ling, T. et al. Engineering surface atomic structure of single-crystal cobalt (ii) oxide nanorods for superior electrocatalysis. Nat. Commun. 7, 12876 (2016).
Yu, Y. et al. High phase-purity 1T′-MoS2- and 1T′-MoSe2-layered crystals. Nat. Chem. 10, 638–643 (2018).
Jaramillo, T. F. et al. Identification of active edge sites for electrochemical H2 evolution from MoS2 nanocatalysts. Science 317, 100–102 (2007).
Li, H. et al. Activating and optimizing MoS2 basal planes for hydrogen evolution through the formation of strained sulphur vacancies. Nat. Mater. 15, 48–53 (2016).
Voiry, D., Yang, J. & Chhowalla, M. Recent strategies for improving the catalytic activity of 2D TMD nanosheets toward the hydrogen evolution reaction. Adv. Mater. 28, 6197–6206 (2016).
Franklin, A. D. Electrocatalysis on Non-metallic Surfaces (National Bureau of Standards, 1975).
Ding, M. et al. An on-chip electrical transport spectroscopy approach for in situ monitoring electrochemical interfaces. Nat. Commun. 6, 7867 (2015).
Ding, M. et al. Nanoelectronic investigation reveals the electrochemical basis of electrical conductivity in Shewanella and Geobacter. ACS Nano 10, 9919–9926 (2016).
Zhang, Y. et al. Chemical vapor deposition of monolayer WS2 nanosheets on Au foils toward direct application in hydrogen evolution. Nano Res. 8, 2881–2890 (2015).
Fujimoto, T. & Awaga, K. Electric-double-layer field-effect transistors with ionic liquids. Phys. Chem. Chem. Phys. 15, 8983–9006 (2013).
Chhowalla, M., Jena, D. & Zhang, H. Two-dimensional semiconductors for transistors. Nat. Rev. Mater. 1, 16052 (2016).
DasA et al. Monitoring dopants by Raman scattering in an electrochemically top-gated graphene transistor. Nat. Nanotechnol. 3, 210–215 (2008).
Braga, D., Gutiérrez Lezama, I., Berger, H. & Morpurgo, A. F. Quantitative determination of the band gap of WS2 with ambipolar ionic liquid-gated transistors. Nano Lett. 12, 5218–5223 (2012).
Ortiz, D. N. et al. Ambipolar transport in CVD grown MoSe2 monolayer using an ionic liquid gel gate dielectric. AIP Adv. 8, 035014 (2018).
Chen, X. et al. Probing the electron states and metal–insulator transition mechanisms in molybdenum disulphide vertical heterostructures. Nat. Commun. 6, 6088 (2015).
Chu, L. et al. Charge transport in ion-gated mono-, bi- and trilayer MoS2 field effect transistors. Sci. Rep. 4, 7293 (2014).
Xia, J., Chen, F., Li, J. & Tao, N. Measurement of the quantum capacitance of graphene. Nat. Nanotechnol. 4, 505–509 (2009).
Lezama, I. G. et al. Single-crystal organic charge-transfer interfaces probed using Schottky-gated heterostructures. Nat. Mater. 11, 788 (2012).
Kaji, T., Takenobu, T., Morpurgo, A. F. & Iwasa, Y. Organic single-crystal Schottky gate transistors. Adv. Mater. 21, 3689–3693 (2009).
Neamen, D. Semiconductor Physics and Devices (McGraw-Hill, 2003).
Xu, Z. J. From two-phase to three-phase: the new electrochemical interface by oxide electrocatalysts. Nano–Micro Lett. 10, 8 (2017).
Suntivich, J., May, K. J., Gasteiger, H. A., Goodenough, J. B. & Shao-Horn, Y. A perovskite oxide optimized for oxygen evolution catalysis from molecular orbital principles. Science 334, 1383–1385 (2011).
Liang, Y. et al. Co3O4 nanocrystals on graphene as a synergistic catalyst for oxygen reduction reaction. Nat. Mater. 10, 780–786 (2011).
Wei, C. et al. Cations in octahedral sites: a descriptor for oxygen electrocatalysis on transition-metal spinels. Adv. Mater. 29, 1606800 (2017).
Liu, Y. et al. Self-optimizing, highly surface-active layered metal dichalcogenide catalysts for hydrogen evolution. Nat. Energy 2, 17127 (2017).
Burke, M. S., Kast, M. G., Trotochaud, L., Smith, A. M. & Boettcher, S. W. Cobalt-iron (oxy)hydroxide oxygen evolution electrocatalysts: the role of structure and composition on activity, stability and mechanism. J. Am. Chem. Soc. 137, 3638–3648 (2015).
Trotochaud, L., Young, S. L., Ranney, J. K. & Boettcher, S. W. Nickel-iron oxyhydroxide oxygen-evolution electrocatalysts: the role of intentional and incidental iron incorporation. J. Am. Chem. Soc. 136, 6744–6753 (2014).
Seh, Z. W. et al. Combining theory and experiment in electrocatalysis: insights into materials design. Science 355, eaad4998 (2017).
Li, S. et al. Halide-assisted atmospheric pressure growth of large WSe2 and WS2 monolayer crystals. Appl. Mater. Today 1, 60–66 (2015).
Huang, J.-H. et al. Large-area 2D layered MoTe2 by physical vapor deposition and solid-phase crystallization in a tellurium-free atmosphere. Adv. Mater. Interfaces 4, 1700157 (2017).
Salvatierra Rodrigo, V. et al. Silicon nanowires and lithium cobalt oxide nanowires in graphene nanoribbon papers for full lithium ion battery. Adv. Energy Mater. 6, 1600918 (2016).
Voiry, D. et al. The role of electronic coupling between substrate and 2D MoS2 nanosheets in electrocatalytic production of hydrogen. Nat. Mater. 15, 1003–1009 (2016).
Wang, J. et al. Field effect enhanced hydrogen evolution reaction of MoS2 nanosheets. Adv. Mater. 29, 1604464 (2017).
This work was supported by MOE under AcRF Tier 1 (M4011782.070 RG4/17 and M4011993.070 RG7/18), AcRF Tier 2 (2015-T2-2-007, 2016-T2-1-131, 2016-T2-2-153 and 2017-T2-2-136) and AcRF Tier 3 (2018-T3-1-002), and the A*Star QTE programme. This work was also supported by MOE under AcRF Tier 1 (2016-T1-002-051, 2017-T1-001-150 and 2017-T1-002-119) and AcRF Tier 2 (2015-T2-2-057, 2016-T2-2-103 and 2017-T2-1-162), and by NTU under Start-Up Grant M4081296.070.500000 in Singapore. H.Z. acknowledges support from ITC via the Hong Kong Branch of National Precious Metals Material Engineering Research Center and a Start-Up Grant from City University of Hong Kong. The authors acknowledge the Facility for Analysis, Characterization, Testing and Simulation, Nanyang Technological University, Singapore for use of their electron microscopy facilities. Q.J.W. acknowledges the support of the Ministry of Education Singapore Grant (MOE2016-T2-1-128) and National Research Foundation–Competitive Research Program (NRF-CRP18-2017-02). Z.Z. acknowledges the support from NSFC (11772153). Z.W.S. acknowledges support from the Institute of Materials Research and Engineering, A*STAR (IMRE/17-1R1211). Work at Rice was supported by the US ARO Grant W911NF-16-1-0255. The authors thank Z.J. Xu for discussions about surface conductance and L. Han, J.R. Galan-Mascaros (Institute of Chemical Research of Catalonia) and P. Tang (Catalonia Institute for Energy Research) for discussions about EIS. The authors also thank Y. Liu (Hunan University) for discussions about the semiconductor electronic device and S. Teddy for XPS measurements and data analysis.
The authors declare no competing interests.
Publisher’s note: Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
About this article
Cite this article
He, Y., He, Q., Wang, L. et al. Self-gating in semiconductor electrocatalysis. Nat. Mater. 18, 1098–1104 (2019). https://doi.org/10.1038/s41563-019-0426-0
This article is cited by
Electrochemical molecular intercalation and exfoliation of solution-processable two-dimensional crystals
Nature Protocols (2023)
Nature Communications (2023)
Nature Protocols (2023)
Electrochemical Energy Reviews (2023)
External-field-driven molecular polarization manipulates reactant interface toward efficient hydrogen evolution
Science China Materials (2023)