Abstract
Scheme 1. Schematic Illustration of the Synthesis and Functionalization of AC
ox
@ImFe
a
a
The carbon matrix (AC), oxidation of AC to form AC
ox
, ligand functionalization, and metal grafting to form AC
ox
@ImFe are Shown. Insets include Raman spectra (D and G bands) after the 8th use, Fourier transform infrared spectroscopy (FT-IR) spectra showing characteristic peaks, SEM image showing the morphology, and the EPR spectrum of the catalyst.
Figure 1. (a) Gas production (
V
H
2
+CO
2
) following successive additions of FA, catalyzed by the AC
ox
@ImFe/PP
3
system vs the control system [AC
ox
/Fe
2+
/PP
3
]. (b) Mapping of the redox potential (
E
h
vs standard hydrogen electrode, SHE) across various stages of the reaction for the catalytic system AC
ox
@ImFe/PP
3
and the control system [AC
ox
/Fe
2+
/PP
3
].
Figure 2. (a) Recyclability of the AC
ox
@ImFe/PP
3
system for the dehydrogenation of FA (data for all of the reuses are shown in
Figure S3a
). (b) Reaction time evolution of
E
h
vs SHE for the [AC
ox
@ImFe/PP
3
/FA] solution. (c) Arrhenius plot demonstrating
E
a
reduction for the catalytic reaction in the 1st, 2nd, and 3rd uses.
Figure 3. (a) Average rates of all uses of the AC
ox
@ImFe/PP
3
catalytic system for the dehydrogenation of FA. (b) TONs and TOFs through consecutive uses. Conditions: [AC
ox
@ImFe] = 15 μmol, [PP
3
] = 7.5 μmol, 7 mL mixture of PC+FA (5/2, ν/ν),
T
= 80 °C (±1), along with continuous addition of FA.
Figure 4. Raman spectra of [AC
ox
@ImFe] (a) before 1st use and (b) after 8th use.
Figure 5. FT-IR spectra of [AC
ox
@ImFe/PP
3
] (a) before 1st use and (b) after the 8th use.
Figure 6. SEM images of (a) AC
ox
, (b) pristine AC
ox
@ImFe, and (c) [AC
ox
@ImFe] after the 8th use.
Figure 7. EPR spectra for [AC
ox
@ImFe] before 1st use and after the 8th use. Experimental conditions:
T
= 77 K, microwave frequency, 9.49 GHz, modulation amplitude, 10 Gpp, and microwave power, 32 mW.
Figure 8. (a) Catalyst resistance in water accumulation vs TONs
normalized
upon consecutive uses of catalyst. (b) Anticorrelation between accumulated water and the mass of catalyst. (c) Schematic illustration showing the evolution of the material’s hydrophilicity and water sensitivity over repeated uses. On the left, during the first use, the material is more sensitive to water (H
2
O) due to its higher hydrophilicity. Over time and with continued use (by the eighth use), the material becomes less hydrophilic and more resilient to water exposure, indicating an improvement in its water resistance properties. The molecular structural modifications associated with this transition are also depicted, highlighting the chemical changes that occur within the material.
