P‐Mediated Cu–N₄ Sites in Carbon Nitride Realizing CO₂ Photoreduction to C₂H₄ with Selectivity Modulation

Abstract

Photocatalytic CO2 reduction to high value‐added C2 products (e.g., C2H4) is of considerable interest but challenging. The C2H4 product selectivity strongly hinges on the intermediate energy levels in the CO2 reduction pathway. Herein, Cu–N4 sites anchored phosphorus‐modulated carbon nitride (CuACs/PCN) is designed as a photocatalyst to tailor the intermediate energy levels in the the C2H4 formation reaction pathway for realizing its high production with tunable selectivity. Theoretical calculations combined with experimental data demonstrate that the formation of the C−C coupling intermediates can be realized on Cu–N4 sites and the surrounding doped P facilitates the production of C2H4. Thus, CuACs/PCN exhibits a high C2H4 selectivity of 53.2% with a yielding rate of 30.51 µmol g−1. The findings reveal the significant role of the coordination environment and surrounding microenvironment of Cu single atoms in C2H4 formation and offer an effective approach for highly selective CO2 photoreduction to produce C2H4.

CoP-Embedded Graphitic N-Doped C Nanosheets in Ohmic Contact with S-Deficient CdS Nanocrystals Triggering Efficient Visible-Light Photocatalytic H2 Evolution

“…The coexistence of Co δ+ and P δ− species reveals the formation of CoP. According to the C 1s spectrum in Figure S8e, the fitted peaks locating at 284.6, 285.9, 286.9, and 288.3 eV reveal the presence of C–C, C–OH, C–O–C, and C–COOH bonds in CoP-CN, respectively. In addition, deconvolution of the N 1s spectrum yields the components at 397.9, 399.2, and 400.4 eV, indicating the formation of pyridinic N, pyrrolic N, and graphitic N, respectively. , (Figure S8f).…”

“…39 The coexistence of Co δ+ and P δ− species reveals the formation of CoP. According to the C 1s spectrum in Figure S8e, the fitted peaks locating at 284.6, 285.9, 286.9, and 288.3 eV reveal the presence of C−C, 40 C−OH, 41 C−O−C, 42 and C− COOH 43 bonds in CoP-CN, respectively. In addition, deconvolution of the N 1s spectrum yields the components The opposite variation of the Cd and Co electron-cloud densities manifests that electrons are transferred from CdS to CoP-CN after their combination, which also hints at the existence of a strong interaction and an intimate heterointerface.…”

Ag as an Electron Mediator in Porous Cu2O Nanostructures for Photocatalytic CO2 Reduction to CO

“…This breakthrough may provide innovative solutions to the energy, environmental, and economic challenges in the world. − Photocatalytic CO 2 reduction is a meaningful strategy that converts CO 2 into high-value hydrocarbon products by using solar energy. Solar energy can efficiently convert CO 2 into various chemical resources such as methane, ethylene, carbon monoxide, and so forth. In recent years, catalysts such as metal oxides (TiO 2 , Cu 2 O, SrTiO 3 , etc.…”

“…), , covalent organic framework materials (COF), , carbon nanomaterials (rGO, C 3 N 4 , etc. ), , MXenes, and single metal atomic catalysts (SACs) ,, have been extensively studied in the field of photocatalytic CO 2 reduction, and the reduction yield has been continuously improved.…”

“…), 16,23 covalent organic framework materials (COF), 19,22 carbon nanomaterials (rGO, C 3 N 4 , etc. ), 17,23 MXenes, and single metal atomic catalysts (SACs) 17,20,24 have been extensively studied in the field of photocatalytic CO 2 reduction, and the reduction yield has been continuously improved. Among the well known semiconductor, p-type cuprous oxide (Cu 2 O) with a band gap of 2.0 eV not only demonstrates a large theoretical photocurrent density of 14.7 mA cm −225−28 but also has a more negative conduction band (CB) for reducing CO 2 to various hydrocarbons.…”