skip to main content
US FlagAn official website of the United States government
dot gov icon
Official websites use .gov
A .gov website belongs to an official government organization in the United States.
https lock icon
Secure .gov websites use HTTPS
A lock ( lock ) or https:// means you've safely connected to the .gov website. Share sensitive information only on official, secure websites.


This content will become publicly available on October 9, 2026

Title: Defect compensation as a strategic approach to enhance photocatalytic water splitting performance of SrTiO 3
Abstract Determining suitable dopants with optimized doping concentration is critical to design efficient water splitting photocatalysts. However, there is currently a lack of fundamental knowledge to guide this process. Herein, we examine the impact of Al3+, Mg2+, and Ga3+on the photocatalytic performance of SrTiO3and propose a defect compensation model to understand the doping effect. Doped SrTiO3crystals were grown hydrothermally and treated in molten SrCl2. The hydrogen production rates from 50 catalysts produced in this way were measured with a high‐throughput parallelized and automated photochemical reactor (PAPCR). The investigation revealed that all three dopants significantly enhance the photocatalytic reactivity. According to Brouwer diagrams computed using available reaction constants, the optimum reactivity is achieved when the concentration of acceptor dopants fully compensates the oxygen vacancy donors. The improved reactivity can be attributed to the reduction in free electron concentration, resulting in a space charge layer that is 1000 times longer. Consequently, this situation enhances the number of photogenerated charge carriers capable of being separated by the band bending and transported to the surface.  more » « less
Award ID(s):
2016267
PAR ID:
10643671
Author(s) / Creator(s):
 ;  ;  
Publisher / Repository:
J. Wiley
Date Published:
Journal Name:
Journal of the American Ceramic Society
ISSN:
0002-7820
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. Abstract Chemical doping is an important approach to manipulating charge-carrier concentration and transport in organic semiconductors (OSCs)1–3and ultimately enhances device performance4–7. However, conventional doping strategies often rely on the use of highly reactive (strong) dopants8–10, which are consumed during the doping process. Achieving efficient doping with weak and/or widely accessible dopants under mild conditions remains a considerable challenge. Here, we report a previously undescribed concept for the photocatalytic doping of OSCs that uses air as a weak oxidant (p-dopant) and operates at room temperature. This is a general approach that can be applied to various OSCs and photocatalysts, yielding electrical conductivities that exceed 3,000 S cm–1. We also demonstrate the successful photocatalytic reduction (n-doping) and simultaneous p-doping and n-doping of OSCs in which the organic salt used to maintain charge neutrality is the only chemical consumed. Our photocatalytic doping method offers great potential for advancing OSC doping and developing next-generation organic electronic devices. 
    more » « less
  2. Abstract Single‐atom catalysts have demonstrated interesting activity in a variety of applications. In this study, we prepared single Co2+sites on graphitic carbon nitride (C3N4), which was doped with carbon for enhanced activity in visible‐light CO2reduction. The synthesized materials were characterized with a variety of techniques, including microscopy, X‐ray powder diffraction, UV‐vis spectroscopy, infrared spectroscopy, photoluminescence spectroscopy, and X‐ray absorption spectroscopy. Doping C3N4with carbon was found to have profound effect on the photocatalytic activity of the single Co2+sites. At relatively low levels, carbon doping enhanced the photoresponse of C3N4in the visible region and improved charge separation upon photoactivation, thereby enhancing the photocatalytic activity. High levels of carbon doping were found to be detrimental to the photocatalytic activity of the single Co2+sites by altering the structure of C3N4and generating defect sites responsible for charge recombination. 
    more » « less
  3. Only when the interfacial charge separation is enhanced and the CO 2 activation is improved, can the heterojunction nanocomposite photocatalyst be brought into full play for the CO 2 reduction reaction (CO 2 RR). Here, Er 3+ single atom composite photocatalysts were successfully constructed based on both the special role of Er 3+ single atoms and the special advantages of the SrTiO 3 :Er 3+ /g-C 3 N 4 heterojunction in the field of photocatalysis for the first time. As we expected, the SrTiO 3 :Er 3+ /g-C 3 N 4 (22.35 and 16.90 μmol g −1 h −1 for CO and CH 4 ) exhibits about 5 times enhancement in visible-light photocatalytic activity compared to pure g-C 3 N 4 (4.60 and 3.40 μmol g −1 h −1 for CO and CH 4 ). In particular, the photocatalytic performance of SrTiO 3 :Er 3+ /g-C 3 N 4 is more than three times higher than that of SrTiO 3 /g-C 3 N 4 . From Er 3+ fluorescence quenching measurements, photoelectrochemical studies, transient PL studies and DFT calculations, it is verified that a small fraction of surface doping of Er 3+ formed Er single-atoms on SrTiO 3 building an energy transfer bridge between the interface of SrTiO 3 and g-C 3 N 4 , resulting in enhanced interfacial charge separation. Aberration-corrected high-angle annular dark-field scanning transmission electron microscopy (AC HAADF-STEM) and adsorption energy calculations demonstrated that the exposed Er single-atoms outside the interface on SrTiO 3 preferentially activate the adsorbed CO 2 , leading to the high photoactivity for the CO 2 RR. A novel enhanced photocatalytic mechanism was proposed, in which Er single-atoms play dual roles of an energy transfer bridge and activating CO 2 to promote charge separation. This provides new insights and feasible routes to develop highly efficient photocatalytic materials by engineering rare-earth single-atom doping. 
    more » « less
  4. Abstract BaTiO3heated in an excess of SrCl2at 1150 °C converts to SrTiO3through an ion exchange reaction. The SrTiO3synthesized by ion exchange produces hydrogen from pH 7 water at a rate more than twice that of conventional SrTiO3treated identically. The apparent quantum yield for hydrogen production in pure water of the ion exchanged SrTiO3is 11.4% under 380 nm illumination. The catalyst resulting from ion‐exchange differs from conventional SrTiO3by having ≈2% residual Ba, inhomogeneous Cl‐doping at a concentration less than 1%, Kirkendall voids in the centers of particles that result from the unequal rates of Sr and Ba diffusion together with the transport of Ti and O, and nanoscale regions near the surface that have lattice spacings consistent with the Sr‐excess phase Sr2TiO4. The increased photochemical efficiency of this nonequilibrium structure is most likely related to the Sr‐excess, which is known to compensate donor defects that can act as charge traps and recombination centers. 
    more » « less
  5. Substitutionally doped transition metal dichalcogenides (TMDs) are essential for advancing TMD‐based field effect transistors, sensors, and quantum photonic devices. However, the impact of local dopant concentrations and dopant–dopant interactions on charge doping and defect formation within TMDs remains underexplored. Here, a breakthrough understanding of the influence of rhenium (Re) concentration is presented on charge doping and defect formation in MoS2monolayers grown by metal–organic chemical vapor deposition (MOCVD). It is shown that Re‐MoS2films exhibit reduced sulfur‐site defects, consistent with prior reports. However, as the Re concentration approaches ⪆2 atom%, significant clustering of Re in the MoS2is observed. Ab Initio calculations indicate that the transition from isolated Re atoms to Re clusters increases the ionization energy of Re dopants, thereby reducing Re‐doping efficacy. Using photoluminescence (PL) spectroscopy, it is shown that Re dopant clustering creates defect states that trap photogenerated excitons within the MoS2lattice, resulting in broad sub‐gap emission. These results provide critical insights into how the local concentration of metal dopants influences carrier density, defect formation, and exciton recombination in TMDs, offering a novel framework for designing future TMD‐based devices with improved electronic and photonic properties. 
    more » « less