ABSTRACT
The design and manufacture of high activity and thermal stability catalysts with minimal precious metal loading is essential for deep degradation of volatile organic compounds (VOCs). In this paper, a novel single-atom Pt-CeO2/Co3O4 catalyst with ultra-low Pt loading capacity (0.06 wt%, denoted as 0.06Pt-SA) was fabricated via one-step co-precipitation method. The 0.06Pt-SA exhibited excellent toluene degradation activity of T90 = 169 °C, matched with the nanoparticle Pt-supported CeO2/Co3O4 catalyst with more than six times higher Pt loading (0.41 wt%, denoted as 0.41Pt-NP). Moreover, the ultra-long durability (toluene conversion remains 99% after 120 h stability test) and excellent toluene degradation ability in a wide space speed range of 0.06Pt-SA were superior to that of 0.41Pt-NP catalyst. The excellent performance was derived from the strong metal-support interaction (SMSI) between the single atomic Pt and the carrier, which induced more Pt0 and Ce3+ for oxygen activation and more Co3+ for toluene removal. The in situdiffuse reflectance infrared spectroscopy (DRIFTS) experiments confirmed that the conversion of intermediates was accelerated in the reaction process, thereby promoting the toluene degradation. Our results should inspire the exploitation of noble single-atomic modification strategy for developing the low cost and high performance VOCs catalyst.
ABSTRACT
Bismuth vanadate (BiVO4) is a prospective candidate for photoelectrochemical (PEC) water oxidation, but its commercial application is limited due to the serious surface charge recombination. In this work, we propose a novel and effective electrochemical reduction strategy combined with co-catalyst modification to manipulate the surface states of the BiVO4 photoanode. Specifically, an ultrathin amorphous structure is formed on the surface of BiVO4 after electrochemical reduction ascribed to the breaking of the surface metal-O bonds. Photoelectrochemical measurements and first-principles calculation show that the electrochemical reduction treatment can effectively reduce the surface energy, thereby passivating the recombined surface states (r-ss) and increasing the mobility of photogenerated holes. In addition, the FeOOH co-catalyst layer further increases the intermediate surface states (i-ss) of BiVO4, stabilizes the surface structure and enhances its PEC performance. Benefiting from the superior charge transfer efficiency and the excellent water oxidation kinetics, the -0.8/BVO/Fe photoanode achieves 2.02 mA cm-2 photocurrent at 1.23 VRHE (2.4 times that of the original BiVO4); meanwhile, the onset potential shifts 90 mV to the cathode. These results provide a new surface engineering tactic to modify the surface states of semiconductor photoanodes for high-efficiency PEC water oxidation.
ABSTRACT
Extracting atmospheric moisture for freshwater production is an appealing way to mitigate the global water crisis. However, the low moisture sorption capacity and high desorption temperature are the major bottlenecks for efficient atmospheric water harvesting. Herein, we develop a transition metal super-hygroscopic hydrogel by an economical strategy, which is constructed through a facile coordination between metal salts and ethanolamine. When the empty electron orbital of the metal ion is coordinated with the lone electron pair of nitrogen or oxygen atom, the water active sorption site is formed. A single water layer is bonded on the sites by a coordination effect, followed by physical interaction with water to form multi-layer structures. The Fe and Co ions in the hydrogel function as dual sorption sites to capture moisture, which can harvest additional water by the synergistic effect of bimetals. As a result, the bimetal hydrogel contributes to a high water uptake of 5.22 g g-1 at 95% RH, triggering the desorption process by one solar intensity due to its low desorption temperature (≤50 °C).
