TY - JOUR
T1 - Ultraviolet assisted defects engineering of metal organic frameworks towards high performance oxygen evolution reaction
AU - Haq, Rana Sami Ul
AU - Lei, Zhihao
AU - Qi, Shuai
AU - Ahmed, Muhammad Ibrar
AU - Perumalsamy, Vibin
AU - Cao, Yitong
AU - Ramadass, Kavitha
AU - Wijerathne, Binodhya
AU - Geng, Xun
AU - Ahmed, Sohail
AU - Hu, Long
AU - Qiao, Liang
AU - Wu, Tom
AU - Yu, Xiaojiang
AU - Breese, Mark B.H.
AU - Zhang, Yong Wei
AU - Yu, Zhi Gen
AU - Yi, Jiabao
N1 - Publisher Copyright:
© 2025 Elsevier B.V.
PY - 2025/11/1
Y1 - 2025/11/1
N2 - Hydrogen production from water splitting has gained tremendous interest as an alternative to fossil fuels, while the sluggish nature of the four-electron process during oxygen evolution reaction (OER) has impeded its practical applications. Here, we report the ultraviolet (UV) assisted OER enhancement of NiFe Prussian blue analogues (PBAs) by the creation and stabilization of new active sites. UV treatment induces the cleavage of certain M-C/M-N (M: Ni or Fe) bonds and the removal of CN groups, thereby increasing the number of active sites. Additionally, due to the breaking of M-C/M-N bonds, OH− functional groups readily bonded to Fe sites, transforming them into active sites that require only three-electrons for the OER process. The optimally treated sample exhibited superior OER performance, with an overpotential of 279 mV, a Tafel slope of 52.0 mV dec−1, a mass activity of 733.33 A g−1 and a turnover frequency of 2.48 s−1 compared to pristine PBA which showed values of 409 mV, 134.6 mV dec−1, 28.83 A g−1, and 0.10 s−1, respectively. Density functional theory (DFT) calculations further confirm lower reaction energy barrier for OER after UV irradiation. Moreover, UV treatment could serve as a universal strategy to enhance the OER performance of other types of metal organic frameworks-based catalysts.
AB - Hydrogen production from water splitting has gained tremendous interest as an alternative to fossil fuels, while the sluggish nature of the four-electron process during oxygen evolution reaction (OER) has impeded its practical applications. Here, we report the ultraviolet (UV) assisted OER enhancement of NiFe Prussian blue analogues (PBAs) by the creation and stabilization of new active sites. UV treatment induces the cleavage of certain M-C/M-N (M: Ni or Fe) bonds and the removal of CN groups, thereby increasing the number of active sites. Additionally, due to the breaking of M-C/M-N bonds, OH− functional groups readily bonded to Fe sites, transforming them into active sites that require only three-electrons for the OER process. The optimally treated sample exhibited superior OER performance, with an overpotential of 279 mV, a Tafel slope of 52.0 mV dec−1, a mass activity of 733.33 A g−1 and a turnover frequency of 2.48 s−1 compared to pristine PBA which showed values of 409 mV, 134.6 mV dec−1, 28.83 A g−1, and 0.10 s−1, respectively. Density functional theory (DFT) calculations further confirm lower reaction energy barrier for OER after UV irradiation. Moreover, UV treatment could serve as a universal strategy to enhance the OER performance of other types of metal organic frameworks-based catalysts.
KW - Electrocatalysis
KW - Hydrogen production
KW - Metal-organic frameworks
KW - Oxygen evolution reaction
KW - Prussian blue analogues
UR - https://www.scopus.com/pages/publications/105016673994
U2 - 10.1016/j.cej.2025.168369
DO - 10.1016/j.cej.2025.168369
M3 - Article
AN - SCOPUS:105016673994
SN - 1385-8947
VL - 523
JO - Chemical Engineering Journal
JF - Chemical Engineering Journal
M1 - 168369
ER -
