Boosting Visible‐Light‐Driven H₂ Evolution of Covalent Triazine Framework from Water by Modifying Ni(II) Pyrimidine‐2‐thiolate Cocatalyst

Abstract

Covalent triazine frameworks (CTFs) have recently emerged as prospective photoactive materials coupled with Pt or Pd cocatalyst for the hydrogen evolution. Herein, we report visible‐light driven hydrogen generation catalyzed by heterogeneous systems combining CTF photosensitizers and a noble‐metal‐free cocatalyst for the first time. CTF‐HC2 was doped with two‐dimensional Ni(II) pyrimidine‐2‐thiolate ([Ni(pymt)2]n) to yield a series of x‐[Ni(pymt)2]n/CTF‐HC2 (x=3, 6, 9, 12, 15, 18 and 24 wt %) composites. Illuminated with λ>420 nm, [Ni(pymt)2]n/CTF‐HC2 materials display excellent photocatalytic performance for H2 generation from water. The highest hydrogen evolution rate is up to 3472 μmol h−1 g−1, which is 68 times of bare CTF‐HC2 (51 μmol h−1 g−1) and 1.16 times of CTF‐HC2 doped 2.0 wt % Pt (2991 μmol h−1 g−1). The efficient and recyclable heterogeneous photocatalytic H2 production from water under visible light has been established.

Crystalline Covalent Triazine Frameworks with Fibrous Morphology via a Low‐Temperature Polycondensation of Planar Monomer

“…[12][13] The CP-MAS 13 C-NMR also unambiguously confirmed the formation of triazine structures in MS-F-CTF-1 samples, where the chemical shifts at 128 and 138 ppm can be assigned to phenyl carbons, and the chemical shift at 170 ppm was assigned to the carbon signal from triazine rings (Figure S7, Supporting Information). [34][35] Furthermore, according to N 1s peak positions of triazine in CTFs, the deconvolution of N 1s peaks around 398.9 eV for both MS-F-CTF-1 and CTF-HUST-HC1 were assigned to pyridinic nitrogen or triazine nitrogen. [12][13] The signals at ≈399.8 to 400.0 eV corresponded to pyrrolic nitrogen coming from the partial decomposition of MS-F-CTF-1 (Figures S8 and S9, Supporting Information).…”

Heteroatom-doped carbon materials derived from covalent triazine framework@MOFs for the oxygen reduction reaction

“…3a shows three peaks at 1512, 1420 and 1368 cm −1 for the CTF, which originated from the triazine ring. 19 And compared to TBPT, the peaks of the CTF were broadened, which may be due to aggregation. 26 In the meantime, the characteristic peaks at 1574 and 1608 cm −1 are assignable to the skeletal vibration of the aromatic rings in the framework.…”

Strategies to improve the photocatalytic performance of covalent triazine frameworks

“…To address this issue, CTFs with nitrogen-rich properties have been applied to serve as a promising support to improve the dispersibility and stability of single-atom catalysts. In recent years, various kinds of single atoms (such as Pt, 188,192 Fe, 193 Ni, 194,195 Pd, 196 Ir, 197 Cu, 189,198 Co, 191,199 Ti, 200 and more) have been anchored on CTFs for various photocatalytic applications. For instance, by constructing CTFs with -N 3 sites, Pt single-atom catalysts have been loaded for photocatalytic N 2 fixation, achieving an ammonia production rate of up to 171.40 μmol g −1 h −1 .…”