In addition to the broad environmental implications associated with the removal of nitroaromatics from industrial effluent, the catalytic reduction of 4‐nitrophenol (4NP) has emerged as a benchmark model for quantifying catalytic activity of metal nanoparticles. Here we present a series of noble metal nanoparticles immobilized on amorphous carbon (Au@C, Ag@C, Pt@C and Pd@C). All materials show competitive catalytic activity over 4NP, amino‐substituted nitrophenols (ANPs) and azo dyes. Overall, Pd@C exhibits superior activity that increases further when exposed to recycling protocol. Moreover, testing all materials synthesized over a broader substrate scope with added functionalities reveals inconsistencies in the prognosticating ability of the ubiquitous 4NP model reaction. By incorporating variably substituted ANPs into the substrate scope and averaging performance, the resulting rank of catalyst activity more accurately reflects activity trends when applied to other reducible functionalities, such as ‐N=N‐ groups in azo dyes.
Gold nanomaterials have widespread applications across multiple areas of science and technology. Sulfur-containing ligands (thiols and thioethers) have been traditionally used as ligands to protect and functionalize these materials. N-Heterocyclic carbenes (NHCs) have recently emerged as organic alternatives to thiols in stabilizing gold nanoparticles (AuNPs) and flat surfaces. In fact, gold-containing materials decorated with NHCs have been shown to withstand a variety of harsh conditions. However, such materials still suffer from limited stability in the presence of thiols, such as the biologically relevant glutathione, in aqueous media. Here, we report the synthesis and application of polymeric mesoionic NHC–Au(I) complexes as precursors to polyNHC-stabilized AuNPs. Using copper-catalyzed alkyne–azide cycloaddition polymerization of diazide- and dialkyne-containing monomers, we directly install 1,2,3-triazole groups, as precursors to mesoionic carbenes, on the backbone of the resulting polymers. This effectively eliminates the need to presynthesize NHC–Au(I)-containing monomers to access this class of polymers. Using these polymers as the substrate, the resulting robust AuNPs, protected by a catenated network of NHCs, demonstrate exceptional stabilities in aqueous media under various conditions, particularly against high concentrations of glutathione (up to 6 mM) for extended periods of time (up to 10 days). Moreover, the use of the macromolecular substrate, compared to small NHC–Au complexes used thus far yielding relatively small AuNPs (∼5 nm), results in the formation of larger AuNPs (∼12 nm). Such enhanced stabilities in aqueous media together with their larger diameters make these materials promising for potential applications in nanomedicine. To highlight their multifunctionality, we also demonstrate their catalytic activity in the reduction of 4-nitrophenol.
Para-, or 4-nitrophenol, and related nitroaromatics are broadly used compounds in industrial processes and as a result are among the most common anthropogenic pollutants in aqueous industrial effluent; this requires development of practical remediation strategies. Their catalytic reduction to the less toxic and synthetically desirable aminophenols is one strategy. However, to date, the majority of work focuses on catalysts based on precisely tailored, and often noble metal-based nanoparticles. The cost of such systems hampers practical, larger scale application. We report a facile route to bulk cobalt oxide-based materials, via a combined mechanochemical and calcination approach. Vibratory ball milling of CoCl2(H2O)6 with KOH, and subsequent calcination afforded three cobalt oxide-based materials with different combinations of CoO(OH), Co(OH)2, and Co3O4 with different crystallite domains/sizes and surface areas; Co@100, Co@350 and Co@600 (Co@###; # = calcination temp). All three prove active for the catalytic reduction of 4-nitrophenol and related aminonitrophenols. In the case of 4-nitrophenol, Co@350 proved to be the most active catalyst, therein its retention of activity over prolonged exposure to air, moisture, and reducing environments, and applicability in flow processes is demonstrated.
Nanoalloys or alloy nanoparticles containing multiple metals are of great interest because the combination of multiple metals in close proximity can grant enhanced properties including stability, activity, and selectivity arising from synergism that cannot be accessed by the combination of individual metals. In this study, we have produced nanoalloys in stable flexible electrospun hydrogel nanofibers composed of poly(acrylic acid) and poly(allylamine hydrochloride). The hydrogel fibers were loaded with metal ions such as copper and silver through an immersion in metal salt solutions followed by a chemical reduction to form the metal nanoparticles. The hydrogel matrix allowed for the absorption of metal ions into the fibers and provided a viscous environment to promote the formation of alloy particles in the small diameter range (<25 nm). The proposed fabrication process is advantageous in terms of simplicity, controllability, and versatility. The reductions of 4-nitrophenol and methylene blue were performed to test and compare the catalytic activity of monometallic nanoparticles and copper−silver bimetallic nanoparticles. The copper−silver bimetallic nanoparticles demonstrated preferred selectivity for the reduction of 4-nitrophenol and higher catalytic activity for the reduction of methylene blue. Overall, we have developed promising stable flexible nanocomposites for catalytic reduction of organic redox compounds, and other catalytic nanoalloy systems could be further studied by modification of the procedure.
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