RESUMEN
The conversion of CO2 to high-value products by renewable energy is a promising approach for realizing carbon neutralization, but the selectivity and efficiency of C2+ products are not satisfying. Herein, we report the controllable preparation of highly ordered mesoporous cobalt oxides with modulated surface states to achieve efficient photothermal water-steam reforming of CO2 to C2 products with high activity and tunable selectivity. Pristine mesoporous Co3O4 exhibited an acetic acid selectivity of 96% with a yield rate of 73.44 µmol g-1 h-1. By rationally modifying mesoporous Co3O4 surface states, mesoporous Co3O4@CoO delivered a radically altered â¼100% ethanol selectivity with a yield rate of 14.85 µmol g-1 h-1. Comprehensive experiments revealed that the pH value could strongly influence the selectivity of C2 products over mesoporous cobalt oxides. Density functional theory verified that reduced surface states and rich oxygen vacancies on surface-modified mesoporous cobalt oxides could facilitate further variation of C2 products from acetic acid to ethanol.
RESUMEN
Aryl sulfones and aryl sulfonamides are of great importance in organic synthesis and medicinal chemistry. Although ortho-C-H functionalization of aryl sulfonyl compounds has been extensively explored, the functionalization of remote meta- and para-C-H bonds is very rare. Herein, we report a tunable meta- and para-selective C-H borylation of aryl sulfonyl compounds enabled by computationally designed ligands and iridium catalyst. This method is capable of accommodating a broad range of substrates under mild reaction conditions. Gram-scale preparation can be achieved with iridium catalyst loading as low as 0.1â mol%. As the introduced boronate group can be easily converted into many other groups, our method provides a general solution to installing functional groups at either meta- or para-position of aryl sulfones and aryl sulfonamides with good to excellent selectivity.
RESUMEN
Electroreduction of CO2 is a sustainable approach to produce syngas with controllable ratios, which are required as specific reactants for the optimization of different industrial processes. However, it is challenging to achieve tunable syngas production with a wide ratio of CO/H2 , while maintaining a high current density. Herein, cadmium sulfoselenide (CdSx Se1-x ) alloyed nanorods are developed, which enable the widest range of syngas proportions ever reported at the current density above 10 mA cm-2 in CO2 electroreduction. Among CdSx Se1-x nanorods, CdS nanorods exhibit the highest Faradaic efficiency (FE) of 81% for CO production with a current density of 27.1 mA cm-2 at -1.2 V vs. reversible hydrogen electrode. With the increase of Se content in CdSx Se1-x nanorods, the FE for H2 production increases. At -1.2 V vs. RHE, the ratios of CO/H2 in products vary from 4:1 to 1:4 on CdSx Se1-x nanorods (x from 1 to 0). Notably, all proportions of syngas are achieved with current density higher than ≈25 mA cm-2 . Mechanistic study reveals that the increased Se content in CdSx Se1-x nanorods strengthens the binding of H atoms, resulting in the increased coverage of H* and thus the enhanced selectivity for H2 production in CO2 electroreduction.
RESUMEN
This study has designed and implemented a library of hetero-nanostructured catalysts, denoted as Pd@Nb2O5, comprised of size-controlled Pd nanocrystals interfaced with Nb2O5 nanorods. This study also demonstrates that the catalytic activity and selectivity of CO2 reduction to CO and CH4 products can be systematically tailored by varying the size of the Pd nanocrystals supported on the Nb2O5 nanorods. Using large Pd nanocrystals, this study achieves CO and CH4 production rates as high as 0.75 and 0.11 mol h-1 gPd-1, respectively. By contrast, using small Pd nanocrystals, a CO production rate surpassing 18.8 mol h-1 gPd-1 is observed with 99.5% CO selectivity. These performance metrics establish a new milestone in the champion league of catalytic nanomaterials that can enable solar-powered gas-phase heterogeneous CO2 reduction. The remarkable control over the catalytic performance of Pd@Nb2O5 is demonstrated to stem from a combination of photothermal, electronic and size effects, which is rationally tunable through nanochemistry.