An Artificial Photosystem of Metal‐Insulator‐CTF Nanoarchitectures for Highly Efficient and Selective CO₂ Conversion to CO

Abstract

It is of pivotal significance to explore robust photocatalysts to promote the photoreduction of CO2 into solar fuels. Herein, an intelligent metal‐insulator‐semiconductor (MIS) nano‐architectural photosystem was constructed by electrostatic self‐assembly between cetyltrimethylammonium bromide (CTAB) insulator‐capped metal Ni nanoparticles (NPs) and covalent triazine‐based frameworks (CTF‐1). The metal‐insulator‐CTF composites unveiled a substantially higher CO evolution rate (1254.15 μmol g−1 h−1) compared with primitive CTF‐1 (1.08 μmol g−1 h−1) and reached considerable selectivity (98.9 %) under visible‐light irradiation. The superior photocatalytic CO2 conversion activity over Ni‐CTAB‐CTF nanoarchitecture could be attributed to the larger surface area, reinforced visible‐light response, and CO2 capture capacity. More importantly, the Ni‐CTAB‐CTF nanoarchitecture endowed the photoexcited electrons on CTF‐1 with the ability to tunnel across the thin CTAB insulating layer, directionally migrating to Ni NPs and thereby leading to the efficient separation of photogenerated electrons and holes in the photosystem. In addition, isotope‐labeled (13CO2) tracer results verified that the reduction products come from CO2 rather than the decomposition of the photocatalysts. This study opens a new avenue for establishing a highly efficient and selective artificial photosystem for CO2 conversion.

Surface ligand-assisted synthesis and biomedical applications of metal–organic framework nanocomposites

“…Hexadecyl trimethyl ammonium bromide (CTAB), as a kind of cationic surfactant, which can interact with nanoparticles through electrostatic absorption and hydrophobic interactions, has been widely used for the assembly of nanostructures. 51,52 Cai and co-authors adopted CTAB as the surface ligand to engineer the electrostatic selfassembly of N-doped MXene/Co-ZIF nanocomposites. 53 The ionic form of CTAB, CTA + , with a highly positive charge, offered a robust capacity to interact with N-doped MXene and MOFs, and thus promoted the self-assembly of MOF nanocomposites (Fig.…”

Strategies for Enhancing the Photocatalytic and Electrocatalytic Efficiency of Covalent Triazine Frameworks for CO2 Reduction

“…Metallized CTFs composites can be synthesized by loading metal-based materials (such as metal nanoparticles, metal oxides and metal hydroxides). [88][89][90][91][92][93] Metallized CTFs composites have a dual advantage containing the advantage of CTFs and the metals as catalytic active sites, which can significantly improve the performance of photocatalytic CO 2 RR. For example, Tian et al [90] successfully prepared a metal-insulatorcovalent triazine-based framework (Ni-CTAB-CTF), which was constructed by insulator-capped metal Ni nanoparticles (NPs), cetyltrimethylammonium bromide (CTAB) and covalent triazinebased frameworks (CTF-1) via a facile impregnation.…”

“…[88][89][90][91][92][93] Metallized CTFs composites have a dual advantage containing the advantage of CTFs and the metals as catalytic active sites, which can significantly improve the performance of photocatalytic CO 2 RR. For example, Tian et al [90] successfully prepared a metal-insulatorcovalent triazine-based framework (Ni-CTAB-CTF), which was constructed by insulator-capped metal Ni nanoparticles (NPs), cetyltrimethylammonium bromide (CTAB) and covalent triazinebased frameworks (CTF-1) via a facile impregnation. The selectivity of the photosystem to produce CO was improved up to 98.9% due to the synergistic effect between catalysts.…”

“…Metallized CTFs composites can be synthesized by loading metal‐based materials (such as metal nanoparticles, metal oxides and metal hydroxides). [ 88–93 ] Metallized CTFs composites have a dual advantage containing the advantage of CTFs and the metals as catalytic active sites, which can significantly improve the performance of photocatalytic CO 2 RR. For example, Tian et al.…”

Insights into Photocatalytic Degradation Pathways and Mechanism of Tetracycline by an Efficient Z-Scheme NiFe-LDH/CTF-1 Heterojunction

“…In the past decade, covalent triazine-based frameworks (CTFs) have received tremendous attention as newly developing organic carbon material for photocatalytic application. Due to the unique features such as tailorable band gap energies, customizable layered structure, and high thermal/chemical stability [ 19 ], CTFs exhibited valuable potential in visible-light-driven photocatalytic environmental remediation [ 20 , 21 ]. It has been demonstrated that the triazine-based-conjugated framework of CTFs is beneficial for broadening their photoresponsive range, and stacking layers structure in CTFs can speed up photoinduced carrier transfer [ 22 ].…”