A NIR‐Responsive Phytic Acid Nickel Biomimetic Complex Anchored on Carbon Nitride for Highly Efficient Solar Hydrogen Production

Abstract

A challenge in photocatalysis consists in improving the efficiency by harnessing a large portion of the solar spectrum. We report the design and realization of a robust molecular-semiconductor photocatalytic system (MSPS) consisting of an earth-abundant phytic acid nickel (PA-Ni) biomimetic complex and polymeric carbon nitride (PCN). The MSPS exhibits an outstanding activity at l = 940 nm with high apparent quantum efficiency (AQE) of 2.8 %, particularly l > 900 nm, as it outperforms all reported state-of-the-art nearinfrared (NIR) hybrid photocatalysts without adding any noble metals. The optimum hydrogen (H 2) production activity was about 52 and 64 times higher with respect to its pristine counterpart under the AM 1.5 G and visible irradiation, respectively, being equivalent to the platinum-assisted PCN. This work sheds light on feasible avenues to prepare highly active, stable, cheap NIR-harvesting photosystems toward sustainable and scalable solar-to-H 2 production.

2D–2D SnS2/Covalent Organic Framework Heterojunction Photocatalysts for Highly Enhanced Solar-Driven Hydrogen Evolution without Cocatalysts

“…It can be seen that S/C-3:7 (τ = 1.42 ns) showed shorter lifespan than that of TpPa-1-COF (τ = 1.74 ns) in Table S3. The charge transfer rate can be calculated using the formula k ET = 1/τ (S/C‑3:7) – 1/τ (TpPa‑1‑COF) ; the calculated result is 1.3 × 10 8 s –1 , revealing that the charge transfer rate is raised in the heterojunction . To further understand the accelerated charge transfer rate of photocatalysts, the electrochemical tests were investigated.…”

“…The charge transfer rate can be calculated using the formula k ET = 1/τ (S/C-3:7) − 1/τ (TpPa-1-COF) ; the calculated result is 1.3 × 10 8 s −1 , revealing that the charge transfer rate is raised in the heterojunction. 71 To further understand the accelerated charge transfer rate of photocatalysts, the electrochemical tests were investigated. Under the on−off cycle irradiation of visible light, the current density of S/C-3:7 is the highest (Figure 5c), which is about threefold as high as that of TpPa-1-COF, manifesting that SnS 2 accelerates the separation of photoelectric hole pairs.…”

Phytate Coordination-Enhanced Electrocatalytic Activity of Copper for Nitroarene Hydrogenation through Concerted Proton-Coupled Electron Transfer

“…The mole of each product (residual nitrobenzene, aniline, azoxybenzene, 1a). 20,24,25 The XRD, SEM, and EDX elemental mapping results (Figure 1b,c and Figure S2) further confirmed the successful coordination of PA on the CF surface with uniform distribution as well as the preserved metallic bulk Cu during the treatments. The highresolution XPS profiles of PA-CF showed the typical signals of Cu, P, and C species (Figure 1d).…”

Iodide ions as invisible chemical scissors tailoring carbon nitride for highly efficient photocatalytic H2O2 evolution

“…The conduction band (CB) potential is very close to the flat band potential in n-type semiconductors. According to the conversion between the standard hydrogen electrode (NHE) and Ag/AgCl electrode, 39 the CB locations of BCN and TCN/NaI 0.4 are ∼1.18 V ( vs. NHE) and ∼1.36 V ( vs. NHE). On the basis of the CB, the valence band (VB) values of BCN and TCN/NaI 0.4 were calculated to be 1.55 V ( vs. NHE) and 1.31 V ( vs. NHE).…”