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Synergy between interface-induced dual active sites ZIF-67@Co-TCTB for enhanced visible-light photocatalytic nitrogen fixation.

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Title: Synergy between interface-induced dual active sites ZIF-67@Co-TCTB for enhanced visible-light photocatalytic nitrogen fixation.
Authors: Bai, Xue1 (AUTHOR), Liu, Li-Ping1 (AUTHOR), Xu, Yi-Fei1 (AUTHOR), Sun, Yu2 (AUTHOR), Sun, Wan-Hong2 (AUTHOR), Deng, Zhe-Peng1 (AUTHOR) dengzp516@163.com, Sun, Yin-Xia1 (AUTHOR) sun_yinxia@163.com, Xu, Li1 (AUTHOR)
Source: Applied Surface Science. Mar2026, Vol. 722, pN.PAG-N.PAG. 1p.
Subjects: Nitrogen fixation, Metal-organic frameworks, Photocatalysis, Visible spectra, Catalytic domains, Photocatalysts, Oxidation-reduction reaction
Abstract: [Display omitted] • A ZIF-67@Co-TCTB composite heterojunction was successfully constructed, introducing dual active sites of Co–N and C O that synergistically enhanced N 2 adsorption and activation. • Optical characterization confirms that photo-generated electrons are directionally transferred from ZIF-67 to Co-TCTB, forming a composite material that significantly suppresses electron-hole recombination and enhances reaction efficiency. • Without sacrificial agents, the ammonia yield reached as high as 199.73 μmol g−1 h−1, and the performance remained stable after four cycles, demonstrating excellent potential for practical application. Photocatalytic nitrogen reduction reaction (PNRR) provides a sustainable pathway for green ammonia synthesis, but still faces challenges such as high photogenerated carrier complexation rate and difficulty in N 2 activation. In this study, ZIF-67@Co-TCTB (ZC-250) MOF-on-MOF composites were prepared by liquid-phase synthesis, aiming at dual active site synergy and interfacial charge behavior modulation to enhance visible light nitrogen fixation performance. Structural and compositional analyses (FT-IR, XRD and XPS) indicate that the composite possesses both Co–N and Co–O coordination environments, and introduces N–Co and C O active sites on the surface, which effectively enhances the N 2 adsorption and activation capacity. Diffuse reflectance spectroscopy (DRS), Mott–Schottky (M–S) and steady-state photoluminescence (PL) characterization revealed that the photogenerated electrons migrated from ZIF-67 to Co-TCTB, which facilitated the interfacial charge separation, and then efficiently reduced the surface adsorbed N 2 to NH 4 +. Under the condition of no sacrificial agent, the NH 4 + yield of ZC-250 was as high as 199.73 μmol g−1 h−1, which was an 8-fold enhancement over that of pure ZIF-67, and showed good stability after four cycles. This study provides a new material design strategy for the construction of MOF-based nitrogen fixation photocatalysts with synergistic active centers and regulated interfacial electronic behavior. [ABSTRACT FROM AUTHOR]
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Database: Engineering Source
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Abstract:[Display omitted] • A ZIF-67@Co-TCTB composite heterojunction was successfully constructed, introducing dual active sites of Co–N and C O that synergistically enhanced N 2 adsorption and activation. • Optical characterization confirms that photo-generated electrons are directionally transferred from ZIF-67 to Co-TCTB, forming a composite material that significantly suppresses electron-hole recombination and enhances reaction efficiency. • Without sacrificial agents, the ammonia yield reached as high as 199.73 μmol g−1 h−1, and the performance remained stable after four cycles, demonstrating excellent potential for practical application. Photocatalytic nitrogen reduction reaction (PNRR) provides a sustainable pathway for green ammonia synthesis, but still faces challenges such as high photogenerated carrier complexation rate and difficulty in N 2 activation. In this study, ZIF-67@Co-TCTB (ZC-250) MOF-on-MOF composites were prepared by liquid-phase synthesis, aiming at dual active site synergy and interfacial charge behavior modulation to enhance visible light nitrogen fixation performance. Structural and compositional analyses (FT-IR, XRD and XPS) indicate that the composite possesses both Co–N and Co–O coordination environments, and introduces N–Co and C O active sites on the surface, which effectively enhances the N 2 adsorption and activation capacity. Diffuse reflectance spectroscopy (DRS), Mott–Schottky (M–S) and steady-state photoluminescence (PL) characterization revealed that the photogenerated electrons migrated from ZIF-67 to Co-TCTB, which facilitated the interfacial charge separation, and then efficiently reduced the surface adsorbed N 2 to NH 4 +. Under the condition of no sacrificial agent, the NH 4 + yield of ZC-250 was as high as 199.73 μmol g−1 h−1, which was an 8-fold enhancement over that of pure ZIF-67, and showed good stability after four cycles. This study provides a new material design strategy for the construction of MOF-based nitrogen fixation photocatalysts with synergistic active centers and regulated interfacial electronic behavior. [ABSTRACT FROM AUTHOR]
ISSN:01694332
DOI:10.1016/j.apsusc.2025.165545