Dimension‐Matched Zinc Phthalocyanine/BiVO₄ Ultrathin Nanocomposites for CO₂ Reduction as Efficient Wide‐Visible‐Light‐Driven Photocatalysts via a Cascade Charge Transfer

Abstract

Cascade charge transfer was realized by aH -bond linked zinc phthalocyanine/BiVO 4 nanosheet (ZnPc/BVNS) composite,w hichs ubsequently works as an efficient widevisible-light-driven photocatalyst for converting CO 2 into CO and CH 4 ,a ss hown by product analysis and 13 Ci sotopic measurement. The optimizedZ nPc/BVNS nanocomposite exhibits ac a. 16-fold enhancement in the quantum efficiency compared with the reported BiVO 4 nanoparticles at the excitation of 520 nm with an assistance of 660 nm photons. Experimental and theoretical results showt he exceptional activities are attributed to the rapid charge separation by acascade Z-scheme charge transfer mechanismformed by the dimension-matched ultrathin (ca. 8nm) heterojunction nanostructure.T he central Zn 2+ in ZnPc could accept the excited electrons from the ligand and then provideacatalytic function for CO 2 reduction. This Z-scheme is also feasible for other MPc,s uch as FePc and CoPc, together with BVNS.

Highly efficient photosynthesis of hydrogen peroxide in ambient conditions

“…The Urbach tail of ZnPPc-NBCN, which were caused by the loading of ZnPPc on NBCN, could enable the utilization of a broader spectrum of visible light (Fig. 2B) (18,19,25). The coordination environment of Zn was characterized via XPS (Fig.…”

“…By contrast, even when it was demonstrated that Z-scheme heterojunctions could also be constructed from two semiconductors with close Fermi levels, their construction seemed more like trial and error, as it is difficult to predict the electron transfer directions (18,19). Fortunately, previous studies showed that the prioritized excitation of the reduction semiconductor in a Z-scheme heterojunction resulted in the type II electron transfer pathway, which indicated that the sufficient excitation of the oxidation semiconductor is extremely important in a Z-scheme heterojunction, especially in the visible-light region, since all desirable artificial photosynthesis systems should be used under solar light (18).…”

Phthalocyanines: An Old Dog Can Still Have New (Photo)Tricks!

“…For instance, Tang and Jing reported the synthesis of an H-bond linked unsubstituted zinc phthalocyanine Pc 19 /BiVO 4 nanosheet composite ( Figure 9 ) [ 122 ], which managed to function as a visible-light-driven photocatalyst for converting CO 2 into CO and CH 4 (under monochromatic beams at 520 and 660 nm), with the Pc presence as cause for a 16-fold increase over the BIVO4 performance (only at 520 nm).…”

Review on Bismuth‐Based Photocatalyst for CO2 Conversion

“…Zinc phthalocyanine (ZnPc) has been paid much attention on as a member of the metal phthalocyanine (MPc) family, Bai et al. reported a ZnPc/BVNS ultrathin nanocomposite (Figure 10f) for CO 2 photoreduction under visible light (Table 1 entry 10) [86] . These ZnPc/BiVO 4 nanocomposites with ultrathin structure as efficient photocatalysts for CO 2 conversion were based on a novel Z‐scheme charge transfer mechanism (Figure 10g).…”