Earth-Abundant-Based Photocatalysts for Efficient and Selective H<sub>2</sub> Production through Reforming of Formic Acid under Visible Light

Hamoud, Houeida Issa; Wolski, Lukasz; Abdelli, Hanen; Chtourou, Radhouane; Lebedev, Oleg; Martin, Christine; Fan, Dong; Maurin, Guillaume; Maignan, Antoine; El-Roz, Mohamad

doi:10.1021/acscatal.3c04690

Cited by 5 publications

(3 citation statements)

References 61 publications

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“…The performance of the most active RuO x @UiO-66(Zr/Ti)-NO 2 sample during photocatalytic CO 2 hydrogenation to CH 4 was further investigated through operando FTIR experiments where both the gas phase products and the surface of the catalyst are analyzed simultaneously in real time under similar irradiation conditions used previously in batch. − The setup is equipped with an online mass spectrometer (MS) and gas chromatography (GC) whereby online injections are taken throughout the reaction. A “Sandwich” cell reactor (Figure a) was used to carry out these experiments where the catalyst is fixed in the cell as a self-supported pallet (20 mg).…”

Section: Resultsmentioning

confidence: 99%

“…These results agree with analogous studies reporting that the use of supported RuO x NPs facilitates chemisorption of CO 2 and their reaction intermediates and promote the (photo)catalytic hydrogenation to methane. 90 − 92 To shed some light on the CO 2 and CO adsorption capacity aver RuO x @UiO-66(Zr/Ti)-NO 2 topic, CO 2 and CO adsorption experiments were conducted under continuous flow of CO 2 /Ar and CO/Ar under operando conditions, and the results were analyzed through FTIR 93 , 94 Initially, different concentrations of CO 2 were introduced in Ar with a total flow rate of 20 cm 3 ·min –1 . It is witnessed that as the concentration of CO 2 increases, the band centered at 2238 cm –1 characteristic of chemisorbed CO 2 increases in a linear way, as illustrated in Figure 12 a.…”

Section: Resultsmentioning

confidence: 99%

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Solar Gas-Phase CO₂ Hydrogenation by Multifunctional UiO-66 Photocatalysts

Rueda-Navarro,

Abou Khalil,

Melillo

et al. 2024

ACS Catal.

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Solar-assisted CO 2 conversion into fuels and chemical products involves a range of technologies aimed at driving industrial decarbonization methods. In this work, we report on the development of a series of multifunctional metal− organic frameworks (MOFs) based on nitro-or amino-functionalized UiO-66(M) (M: Zr or Zr/Ti) supported RuO x NPs as photocatalysts, having different energy band level diagrams, for CO 2 hydrogenation under simulated concentrated sunlight irradiation. RuO x (1 wt %; 2.2 ± 0.9 nm)@UiO-66(Zr/Ti)-NO 2 was found to be a reusable photocatalyst, to be selective for CO 2 methanation (5.03 mmol g −1 after 22 h;, apparent quantum yield at 350, 400, and 600 nm of 1.67, 0.25, and 0.01%, respectively), and to show about 3−6 times activity compared with previous investigations. The photocatalysts were characterized by advanced spectroscopic techniques like femto-and nanosecond transient absorption, spin electron resonance, and photoluminescence spectroscopies together with (photo)electrochemical measurements. The photocatalytic CO 2 methanation mechanism was assessed by operando FTIR spectroscopy. The results indicate that the most active photocatalyst operates under a dual photochemical and photothermal mechanism. This investigation shows the potential of multifunctional MOFs as photocatalysts for solar-driven CO 2 recycling.

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Solar Gas-Phase CO₂ Hydrogenation by Multifunctional UiO-66 Photocatalysts

Rueda-Navarro,

Abou Khalil,

Melillo

et al. 2024

ACS Catal.

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“…Recent years have witnessed the development of heterogeneous catalysts for the formic acid-based hydrogen storage system. − Several strategies have been proposed to obtain the remarkable activity and selectivity of catalysts for formic acid dehydrogenation. − The first strategy is optimizing particle size and composition of the metal particles. Jiang and co-workers proved that the surface energy of metal particles regulates the adsorption energy of HCOOH, influencing the activity of catalysts.…”

Section: Introductionmentioning

confidence: 99%

Engineering the Microstructure at Co Single-Atom Sites by Co Nanoparticles Core for Enhanced Formic Acid Selective Dehydrogenation

Zhang,

Zu,

Mao

et al. 2024

ACS Sustainable Chem. Eng.

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The liquid hydrogen storage material, formic acid, is a promising solution to utilize hydrogen energy safely and efficiently. However, a low-cost and efficient catalyst for formic acid dehydrogenation is needed to build such a formic acid-based hydrogen storage system. Based on cheap non-noble metal, we constructed a cobalt catalyst with hybrid core−shell structural active sites, which significantly promote formic acid selective dehydrogenation from 200 to 1619 mL g −1 h −1 and suppress the carbon monoxide formation from 1644 to 92 ppm. Such a hybrid core−shell structure consists of single atomic Co sites anchored carbon layers shell and Co nanoparticle core. The hybrid structure has excellent antiacid leaching stability to catalyze neat formic acid decomposition. The density functional theory calculations reveal that the changes in microstructure at single atomic Co sites optimize the adsorption energy of the intermediate, resulting in a lower dehydrogenation energy barrier and a higher dehydration energy barrier.

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Formic Acid Dehydration Using Mechanochemically Prepared TiO₂‐Graphite Composites

Yruela‐Garrido,

Martín‐Rodríguez,

Castillejos

et al. 2024

ChemCatChem

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Commercial high surface area graphite (HSAG300) and commercial TiO2 were used to produce composite materials through a simple mechanochemical method involving milling and ultrasonic treatments. The acid and basic sites exposed on the surfaces of these materials were characterized by temperature‐programmed desorption (TPD) of ammonia and carbon dioxide. The catalytic materials were tested in the dehydration reaction of formic acid to produce hydrogen‐free CO. While HSAG300 is practically inactive under reaction conditions (continuous gas flow at temperatures in the range of 100‐250 ºC), all samples containing TiO2 are active, exhibiting high selectivity to CO without significant deactivation at moderate reaction temperatures. It is demonstrated that the presence of graphite in the catalysts enhances the specific catalytic activity of TiO2. Assuming that the dehydration reaction is catalyzed by acid sites on the TiO2 surfaces, a comparative evaluation of the surface sites reveals that the graphite‐TiO2 interactions not only change the density of surface sites but also modify the strength of the acid centers of TiO2. In summary, the interaction of HSAG300 with TiO2 modulates the surface properties of the prepared composite catalysts, decreasing the total number of basic surface sites and increasing the strength of acidic sites compared to bare TiO2.

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Earth-Abundant-Based Photocatalysts for Efficient and Selective H₂ Production through Reforming of Formic Acid under Visible Light

Cited by 5 publications

References 61 publications

Solar Gas-Phase CO₂ Hydrogenation by Multifunctional UiO-66 Photocatalysts

Solar Gas-Phase CO₂ Hydrogenation by Multifunctional UiO-66 Photocatalysts

Engineering the Microstructure at Co Single-Atom Sites by Co Nanoparticles Core for Enhanced Formic Acid Selective Dehydrogenation

Formic Acid Dehydration Using Mechanochemically Prepared TiO₂‐Graphite Composites

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Earth-Abundant-Based Photocatalysts for Efficient and Selective H2 Production through Reforming of Formic Acid under Visible Light

Cited by 5 publications

References 61 publications

Solar Gas-Phase CO2 Hydrogenation by Multifunctional UiO-66 Photocatalysts

Solar Gas-Phase CO2 Hydrogenation by Multifunctional UiO-66 Photocatalysts

Engineering the Microstructure at Co Single-Atom Sites by Co Nanoparticles Core for Enhanced Formic Acid Selective Dehydrogenation

Formic Acid Dehydration Using Mechanochemically Prepared TiO2‐Graphite Composites

Contact Info

Product

Resources

About

Earth-Abundant-Based Photocatalysts for Efficient and Selective H₂ Production through Reforming of Formic Acid under Visible Light

Solar Gas-Phase CO₂ Hydrogenation by Multifunctional UiO-66 Photocatalysts

Solar Gas-Phase CO₂ Hydrogenation by Multifunctional UiO-66 Photocatalysts

Formic Acid Dehydration Using Mechanochemically Prepared TiO₂‐Graphite Composites