Graphitic carbon nitrides as platforms for single-atom photocatalysis.

Herein we demonstrate that adding single atoms of selected transition metals to graphitic carbon nitrides allows the tailoring of the electronic and chemical properties of these 2D nanomaterials, directly impacting their usage in photocatalysis. These single-atom photocatalysts were successfully prepared with Ni2+, Pt2+ or Ru3+ by cation exchange, using poly(heptazine imides) (PHI) as the 2D layered platform. Differences in photocatalytic performance for these metals were assessed using rhodamine-B (RhB) and methyl orange (MO) as model compounds for degradation. We have demonstrated that single atoms may either improve or impair the degradation of RhB and MO, depending on the proper matching of the net charge of these molecules and the surface potential of the catalyst, which in turn is responsive to the metal incorporated into the PHI nanostructures. Computer simulations demonstrated that even one transition metal cation caused dramatic changes in the electronic structure of PHI, especially regarding light absorption, which was extended all along the visible up to the near IR region. Besides introducing new quantum states, the metal atoms strongly polarized the molecular orbitals across the PHI and electrostatic fields arising from the electronic transitions became at least tenfold stronger. This simple proof of concept demonstrates that these new materials hold promise as tools for many important photocatalytic reactions that are strongly dependent on our ability to control surface charge and its polarization under illumination, such as H2 evolution, CO2 reduction and photooxidation in general.

Experimental Evidence of CO2 Photoreduction Activity of SnO2 Nanoparticles.

Tin dioxide (SnO2 ) has intrinsic characteristics that do not favor its photocatalytic activity. However, we evidenced that surface modification can positively influence its performance for CO2 photoreduction in the gas phase. The hydroxylation of the SnO2 surface played a role in the CO2 affinity decreasing its reduction potential. The results showed that a certain selectivity for methane (CH4 ), carbon monoxide (CO), and ethylene (C2 H4 ) is related to different SnO2 hydrothermal annealing. The best performance was seen for SnO2 annealed at 150 °C, with a production of 20.4 µmol g-1 for CH4 and 16.45 µmol g-1 for CO, while for SnO2 at 200 °C the system produced more C2 H4 , probably due to a decrease of surface -OH groups.

Cobalt Oxide on Boron-Doped Graphitic Carbon Nitride as Bifunctional Photocatalysts for CO2 Reduction and Hydrogen Evolution.

In this work, the prepared cobalt oxide decorated boron-doped g-C3N4 (CoOx/g-C3N4) heterojunction exhibits remarkable activity in CO2 reduction (CO2RR), resulting in high yields of CH3COOH (∼383 µmol·gcatalyst-1) and CH3OH (∼371 µmol·gcatalyst-1) with 58% selectivity to C2+ under visible light. However, the same system leads to high H2 evolution (HER) by increasing the cobalt oxide content, suggesting that the selectivity and preference for the CO2RR or HER depend on oxide decoration. By comparing HER and CO2RR evolution in the same system, this work provides critical insights into the catalytic mechanism, indicating that the CoOx/g-C3N4 heterojunction formation is necessary to foster high visible light photoactivity.

Insights into the role of CuO in the CO2 photoreduction process.

The CO2 photoreduction process to produce light hydrocarbons is known to be influenced by the presence of CuO nanoparticles, but the actual role of this material, whether as a catalyst or a reactant, has not yet been revealed. In this work, we investigate the role of CuO nanoparticles produced by a solvothermal method as a catalyst in CO2-saturated water reaction media under UV light, considering the effects of different electrolytes (Na2C2O4, KBrO3, and NaOH) and temperatures on nanoparticle phase and activity. The electrolyte strongly influenced product selectivity (NaOH led to evolution of CH4, Na2C2O4 to CO, and KBrO3 to O2) and induced CuO phase change. A long-term analysis of these processes indicated that during the initial steps, CuO acted as a reactant, rather than as a catalyst, and was converted to CuCO3.Cu(OH)2, while the as-converted material acted as a catalyst in CO2 photoreduction, with conversion values comparable to those reported in the literature.