Maximizing Photoelectrochemical Performance in Metal‐Oxide Hybrid Composites via Amorphous Exsolution—A New Exsolution Mechanism for Heterogeneous Catalysis

• Published in: Small (Weinheim an der Bergstrasse, Germany) Germany), 2024-05, Vol.20 (18), p.e2308934-n/a
• Main Authors: Kim, Myeong‐Jin, Hassan, Mostafa Afifi, Lee, Changhoon, Jung, Wan‐Gil, Bae, Hyojung, Jeon, SungHyun, Jung, WooChul, Ha, Jun‐Seok, Shim, Ji Hoon, Park, Jae‐Hoon, Ryu, Sang‐Wan, Kim, Bong‐Joong
• Format: Article
• Language: English
• Subjects: amorphous state; Bonding strength; Charge transfer; Crystallization; Dopants; Doping; exsolution; High temperature; hybrid composite; Hybrid composites; in situ transmission electron microscopy; Interface stability; Mathematical analysis; Nanoparticles; Performance enhancement; Perovskites; Photoanodes; photoelectrochemical water splitting; Strontium titanates; Structural stability; Surface stability; Water splitting
• ISSN: 1613-6810; 1613-6829
• DOI: 10.1002/smll.202308934

Exsolution generates metal nanoparticles anchored within crystalline oxide supports, ensuring efficient exposure, uniform dispersion, and strong nanoparticle–perovskite interactions. Increased doping level in the perovskite is essential for further enhancing performance in renewable energy applications; however, this is constrained by limited surface exsolution, structural instability, and sluggish charge transfer. Here, hybrid composites are fabricated by vacuum‐annealing a solution containing SrTiO3 photoanode and Co cocatalyst precursors for photoelectrochemical water‐splitting. In situ transmission electron microscopy identifies uniform, high‐density Co particles exsolving from amorphous SrTiO3 films, followed by film‐crystallization at elevated temperatures. This unique process extracts entire Co dopants with complete structural stability, even at Co doping levels exceeding 30%, and upon air exposure, the Co particles embedded in the film oxidize to CoO, forming a Schottky junction at the interface. These conditions maximize photoelectrochemical activity and stability, surpassing those achieved by Co post‐deposition and Co exsolution from crystalline oxides. Theoretical calculations demonstrate in the amorphous state, dopant─O bonds become weaker while Ti─O bonds remain strong, promoting selective exsolution. As expected from the calculations, nearly all of the 30% Fe dopants exsolve from SrTiO3 in an H2 environment, despite the strong Fe─O bond's low exsolution tendency. These analyses unravel the mechanisms driving the amorphous exsolution. A method is devised to exsolve dopants from the amorphous state of perovskite oxide, followed by crystallization of the oxide through vacuum‐annealing at elevated temperatures. This process extracts all Co atoms heavily doped into SrTiO3, resulting in the formation of uniformly distributed high‐density CoO particles embedded in the support, with complete structural stability, dramatically enhancing photoelectrochemical (PEC) performances.