TY - JOUR
T1 - Fabrication of site activated and synergistic double vacancy ZnIn2S4 for highly efficient bifunctional photocatalysis
T2 - nitrogen reduction and oxidative degradation
AU - Xia, Shengjie
AU - Yuan, Ziying
AU - Meng, Yue
AU - Zhang, Chen
AU - Li, Xianglong
AU - Ni, Zheming
AU - Zhang, Xueqiang
N1 - Publisher Copyright:
© 2024 The Royal Society of Chemistry.
PY - 2023/12/19
Y1 - 2023/12/19
N2 - A novel methodology harnessing the synergistic influence of bimetallic and non-metallic dual vacancies within a unified catalyst for enabling highly efficient bifunctional photocatalysis encompassing oxidation and reduction processes is presented. ZnIn2S4, engineered to possess concurrent zinc and sulfur dual vacancies (ZnIn2S4-VZn+S), underwent synthesis and rigorous characterization employing atomic-resolution HAADF-STEM. This tailored catalyst was subsequently employed for pivotal photocatalytic processes, including nitrogen reduction (pNRR) and the photooxidative degradation of hexachlorobenzene (HCB). Computational analyses using Density Functional Theory (DFT) unveiled site-specific activation facilitated by Zn and S dual vacancies, activating water molecules and nitrogen, culminating in a synergistic effect driving ammonia synthesis. Additionally, X-ray Absorption Near Edge Structure (XANES) spectroscopy elucidated the role of photogenerated electrons confined within the sulfur vacancy, utilizing In3+ as an intermediary for electron migration, instigating a reaction with N2 to yield NH3 (In3+-N2 + H+ + VS(e−) → In2+ + NH3), further augmenting the collaborative effect of dual vacancies on nitrogen reduction. Furthermore, the Zn and S vacancies emerged as active sites for hydroxyl and superoxide radical generation, facilitating enhanced participation of photogenerated carriers in radical generation reactions. This distinctive electron aggregation pathway engendered significant synergy, markedly enhancing the photodegradation prowess. Thus, the observed synergistic effect of site activation between Zn and S vacancies yielded a cumulative effect surpassing individual contributions (1 + 1 ≫ 2), thereby facilitating efficient photoreduction and photooxidation.
AB - A novel methodology harnessing the synergistic influence of bimetallic and non-metallic dual vacancies within a unified catalyst for enabling highly efficient bifunctional photocatalysis encompassing oxidation and reduction processes is presented. ZnIn2S4, engineered to possess concurrent zinc and sulfur dual vacancies (ZnIn2S4-VZn+S), underwent synthesis and rigorous characterization employing atomic-resolution HAADF-STEM. This tailored catalyst was subsequently employed for pivotal photocatalytic processes, including nitrogen reduction (pNRR) and the photooxidative degradation of hexachlorobenzene (HCB). Computational analyses using Density Functional Theory (DFT) unveiled site-specific activation facilitated by Zn and S dual vacancies, activating water molecules and nitrogen, culminating in a synergistic effect driving ammonia synthesis. Additionally, X-ray Absorption Near Edge Structure (XANES) spectroscopy elucidated the role of photogenerated electrons confined within the sulfur vacancy, utilizing In3+ as an intermediary for electron migration, instigating a reaction with N2 to yield NH3 (In3+-N2 + H+ + VS(e−) → In2+ + NH3), further augmenting the collaborative effect of dual vacancies on nitrogen reduction. Furthermore, the Zn and S vacancies emerged as active sites for hydroxyl and superoxide radical generation, facilitating enhanced participation of photogenerated carriers in radical generation reactions. This distinctive electron aggregation pathway engendered significant synergy, markedly enhancing the photodegradation prowess. Thus, the observed synergistic effect of site activation between Zn and S vacancies yielded a cumulative effect surpassing individual contributions (1 + 1 ≫ 2), thereby facilitating efficient photoreduction and photooxidation.
UR - http://www.scopus.com/inward/record.url?scp=85181667830&partnerID=8YFLogxK
U2 - 10.1039/d3ta05144g
DO - 10.1039/d3ta05144g
M3 - Article
AN - SCOPUS:85181667830
SN - 2050-7488
VL - 12
SP - 2294
EP - 2308
JO - Journal of Materials Chemistry A
JF - Journal of Materials Chemistry A
IS - 4
ER -