Reduction Of 4-nitrothiophenol Research Articles

Au-on-Ag nanostructure for in-situ SERS monitoring of catalytic reactions

Dual-functionality Au-on-Ag nanostructures (AOA) were fabricated on a silicon substrate by first immobilizing citrate-reduced Ag nanoparticles (Ag NPs, ∼43 nm in diameter), followed by depositing ∼7 nm Au nanofilms (Au NFs) via thermal evaporation. Au NFs were introduced for their catalytic activity in concave-convex nano-configuration. Ag NPs underneath were used for their significant enhancement factor (EF) in surface-enhanced Raman scattering (SERS)-based measurements of analytes of interest. Rhodamine 6G (R6G) was utilized as the Raman-probe to evaluate the SERS sensitivity of AOA. The SERS EF of AOA is ∼37 times than that of Au NPs. Using reduction of 4-nitrothiophenol (4-NTP) by sodium borohydride (NaBH4) as a model reaction, we demonstrated the robust catalytic activity of AOA as well as its capacity to continuously monitor via SERS the disappearance of reactant 4-NTP, emergence and disappearance of intermediate 4,4′-DMAB, and the appearance of product 4-ATP throughout the reduction process in real-time and in situ.

Effective fabrication of porous Au-Ag alloy nanorods for in situ Raman monitoring catalytic oxidation and reduction reactions

Porous metal nanostructures exhibit excellent catalytic properties due to their high surface-to-volume ratios and abundant catalytic active sites. However, it is still challenging to control nanopores density and structural features in a facile route and the preparation of porous alloy nanorods for catalytic application has not been well explored. In this work, we demonstrate a synthetic strategy to fabricate highly porous Au–Ag alloy nanorods (P-AuAgNRs) by critically dealloying Ag atoms from homogeneous solid Au–Ag alloy nanorods (AuAgNRs). Combining the merits of the tunable plasmonic properties of noble metal nanorods, excellent stabilities of alloys, and superior catalytic activities of porous structures, we use the P-AuAgNRs as a Raman probe for the in situ monitoring of the catalytic oxidation of 3,3’,5,5’ tetramethylbenzidine (TMB) and reduction of 4-nitrothiophenol (4-NTP). We also compare their composition-dependent catalytic activities. The results show that P-AuAgNRs possess superior chemical stability and higher catalytic activity than those of core-shell structures due to synergistic structural and chemical mechanisms. This strategy provides a predictive design approach for the next-generation alloy catalysts with high-performance.

Interaction of 4-nitrothiophenol with low energy electrons: Implications for plasmon mediated reactions.

The reduction of 4-nitrothiophenol (NTP) to 4-4'-dimercaptoazobenzene (DMAB) on laser illuminated noble metal nanoparticles is one of the most widely studied plasmon mediated reactions. The reaction is most likely triggered by a transfer of low energy electrons from the nanoparticle to the adsorbed molecules. Besides the formation of DMAB, dissociative side reactions of NTP have also been observed. Here, we present a crossed electron-molecular beam study of free electron attachment to isolated NTP in the gas-phase. Negative ion yields are recorded as a function of the electron energy, which helps to assess the accessibility of single electron reduction pathways after photon induced electron transfer from nanoparticles. The dominant process observed with isolated NTP is associative electron attachment leading to the formation of the parent anion of NTP. Dissociative electron attachment pathways could be revealed with much lower intensities, leading mainly to the loss of functional groups. The energy gained by one electron reduction of NTP may also enhance the desorption of NTP from nanoparticles. Our supporting experiments with small clusters, then, show that further reaction steps are necessary after electron attachment to produce DMAB on the surfaces.

Au@Ag nanorod horizontal arrays: Self-assembly preparation and in situ monitoring SERS of plasmonic catalytic reaction

Abstract Here, we successfully synthesized silver-coated gold nanorods (Au@Ag NRs) via a facile wet chemical method. The catalytic property of Au@Ag NRs in water solution was much better than that of Au NRs in water solution. To obtain high catalytic properties, we self-assembled a single-layer Au@Ag NR array by evaporation on a silicon wafer. The catalytic activity of the Au@Ag NR array was probed using the reduction of 4-nitrothiophenol. The reaction processes were monitored and identified through in situ surface-enhanced Raman spectroscopy based on the confocal Raman microscope system. This study provides a simple and fast method to improve the catalytic property of the noble nanoparticles.

Bifunctional Metal Nanocrystals for Catalyzing and Reporting on Chemical Reactions.

Bifunctional nanocrystals with integrated plasmonic and catalytic activities hold great promise for analyzing chemical reactions by in situ surface-enhanced Raman spectroscopy. This Minireview gives a brief introduction to the general strategies for designing such nanocrystals, followed by four typical examples, including their fabrication, characterization, and potential limitation. We then use the reduction of 4-nitrothiophenol and oxidation of 4-aminothiophenol as two model systems to demonstrate the capabilities of these bifunctional nanocrystals to monitor chemical reactions for the elucidation of reaction mechanisms and measurement of kinetics. We conclude with perspectives on further development of these bifunctional nanocrystals into a viable platform for investigating other types of catalytic reactions.

SERS detection of heterogeneous reactions at catalytic interfaces using bifunctional metal nanoparticles

Insight into the molecular changes at catalytic interfaces is of fundamental importance not only for understanding reaction mechanism but also for rational design of high-efficient catalysts. Surface-enhanced Raman scattering (SERS) is a sensitive spectroscopic technique which could be used in label-free monitoring of the molecular transformations on noble metals. This review introduces the synthesis of bifunctional metal nanoparticles comprising both SERS-active and catalytically-active metals. The use of the bifunctional nanoparticles in SERS monitoring of metal-catalyzed chemical reactions, such as the reduction of 4-nitrothiophenol, the photocatalytic oxidation of 4-aminothiophenol and the oxidation of carbon monoxide, is summarized. Finally, the limitations of SERS study of conventional catalytic reactions are discussed and the possible future development is prospected.

Ag-Au alloy nanoparticles: Synthesis and in situ monitoring SERS of plasmonic catalysis

Noble metal nanostructures are currently of great interest for their unique plasmonic property and potential applications in catalysis and surface-enhanced spectroscopy. However, the application of plasmonic nanostructures for quantitatively in situ SERS monitoring of the catalytic reaction has been a great challenge for investigators because combining plasmonics with catalysis requires the same kind of noble metal nanoparticles (NPs) in two very different size regimes. Herein, We have demonstrated a facile wet chemical method to synthesize Au-Ag alloy plasmonic NPs that could combine the desired plasmonic and catalytic properties with same NPs. The catalytic activity of Au-Ag alloy NPs using the reduction of 4-nitrothiophenol (4-NTP) by sodium borohydride (NaBH4) is chosen as a model reaction. The signals of the reaction processes are detected and identified through in situ SERS spectroscopy with high sensitivity. The insights gained by current study may serve as a promising and powerful technique for better investigation in the heterogeneous catalysis. Moreover, the reduction of aromatic nitro compounds with prepared Au-Ag alloy NPs also provides potential application in sewage treatment.

Controlling the Catalytic Efficiency on the Surface of Hollow Gold Nanoparticles by Introducing an Inner Thin Layer of Platinum or Palladium

The efficiency of heterogeneous catalysis of electron-transfer reactions on the surface of gold nanoshells was changed by adding an inner platinum or palladium nanoshell in the double-shell nanocatalysts. The reduction of 4-nitrothiophenol (4NTP) by borohydride was studied as a model reaction. To confirm the heterogeneous catalytic mechanism, the nanocatalysts were assembled into a monolayer on the surface of a quartz substrate using the Langmuir-Blodgett technique, and the 4NTP was allowed to bind to the surface of gold through a strong thiol bond. The stages of the reduction reaction of 4NTP on the surface of gold were successfully followed by time-resolved surface-enhanced Raman spectroscopy. Palladium was found to increase the catalytic efficiency of the gold surface due to the presence of a new Fermi level of the palladium-gold alloy, while platinum decreased its catalytic efficiency due to the electron-withdrawing effect of platinum atoms, which resulted from the difference in their electrochemical reduction potentials.

Galvanic replacement approach for bifunctional polyacrylonitrile/Ag–M (M = Au or Pd) nanofibers as SERS-active substrates for monitoring catalytic reactions

SERS has been applied to monitor different types of catalytic reactions on the surface of metal NPs in recent years, which requires bifunctional metal structures with plasmonic properties as well as catalytic activity. Monitoring catalytic reactions with SERS technology in previous reports was usually performed in metal solution, using metal electrodes or on a glass/silica substrate with an immobilized metal. Here, we report a general approach for preparing novel SERS-active substrates which are used to monitor catalytic reactions. The polyacrylonitrile (PAN)/Ag–M (M = Au or Pd) bimetallic nanofibrous mats are prepared through galvanic replacement reactions of Ag with Au or Pd on the surface of electrospun PAN/Ag nanofibers. The composition of Ag and Au or Pd could be tuned by changing the concentration of the metal solution used for replacement. The PAN/Ag0.60Au0.40 and PAN/Ag0.90Pd0.10 bimetallic nanofibrous mats exhibit both excellent SERS and catalytic activities. The reduction of 4-nitrothiophenol (4-NTP) to the corresponding to 4-aminothiophenol (4-ATP) on PAN/Ag0.60Au0.40 and PAN/Ag0.90Pd0.10 bimetallic nanofibrous mats are monitored by SERS technology. The SERS signals of the reaction intermediate, 4,4′-dimercapto-azobenzene(4,4′-DMAB), are observed as the reaction proceeds with time.