Douglas R. Kauffman

CARBON NANOTUBE GAS AND VAPOR SENSORS

Carbon nanotubes have aroused great interest since their discovery in 1991. Because of the vast potential of these materials, researchers from diverse disciplines have come together to further develop our understanding of the fundamental properties governing their electronic structure and susceptibility towards chemical reaction. Carbon nanotubes show extreme sensitivity towards changes in their local chemical environment that stems from the susceptibility of their electronic structure to interacting molecules. This chemical sensitivity has made them ideal candidates for incorporation into the design of chemical sensors. Towards this end, carbon nanotubes have made impressive strides in sensitivity and chemical selectivity to a diverse array of chemical species. Despite the lengthy list of accomplishments, several key challenges must be addressed before carbon nanotubes are capable of competing with state-of-the-art solid-state sensor materials. The development of carbon nanotube based sensors is still in its infancy, but continued progress may lead to their integration into commercially viable sensors of unrivalled sensitivity and vanishingly small dimensions.

Electrocatalytic Activity of Nitrogen-Doped Carbon Nanotube Cups

The electrochemical activity of stacked nitrogen-doped carbon nanotube cups (NCNCs) has been explored in comparison to commercial Pt-decorated carbon nanotubes. The nanocup catalyst has demonstrated comparable performance to that of Pt catalyst in oxygen reduction reaction. In addition to effectively catalyzing O(2) reduction, the NCNC electrodes have been used for H(2)O(2) oxidation and consequently for glucose detection when NCNCs were functionalized with glucose oxidase (GOx). Creating the catalysts entirely free of precious metals is of great importance for low-cost fuel cells and biosensors.

Experimental and Computational Investigation of Au25 Clusters and CO2: A Unique Interaction and Enhanced Electrocatalytic Activity

Atomically precise, inherently charged Au(25) clusters are an exciting prospect for promoting catalytically challenging reactions, and we have studied the interaction between CO(2) and Au(25). Experimental results indicate a reversible Au(25)-CO(2) interaction that produced spectroscopic and electrochemical changes similar to those seen with cluster oxidation. Density functional theory (DFT) modeling indicates these changes stem from a CO(2)-induced redistribution of charge within the cluster. Identification of this spontaneous coupling led to the application of Au(25) as a catalyst for the electrochemical reduction of CO(2) in aqueous media. Au(25) promoted the CO(2) → CO reaction within 90 mV of the formal potential (thermodynamic limit), representing an approximate 200-300 mV improvement over larger Au nanoparticles and bulk Au. Peak CO(2) conversion occurred at -1 V (vs RHE) with approximately 100% efficiency and a rate 7-700 times higher than that for larger Au catalysts and 10-100 times higher than those for current state-of-the-art processes.

Understanding the sensor response of metal-decorated carbon nanotubes

We have explored the room temperature response of metal nanoparticle decorated single-walled carbon nanotubes (NP-SWNTs) using a combination of electrical transport, optical spectroscopy, and electronic structure calculations. We have found that upon the electrochemical growth of Au NPs on SWNTs, there is a transfer of electron density from the SWNT to the NP species, and that adsorption of CO molecules on the NP surface is accompanied by transfer of electronic density back into the SWNT. Moreover, the electronic structure calculations indicate dramatic variations in the charge density at the NP-SWNT interface, which supports our previous observation that interfacial potential barriers dominate the electrical behavior of NP-SWNT systems.

Tuning the Magic Size of Atomically Precise Gold Nanoclusters via Isomeric Methylbenzenethiols

Toward controlling the magic sizes of atomically precise gold nanoclusters, herein we have devised a new strategy by exploring the para-, meta-, ortho-methylbenzenethiol (MBT) for successful preparation of pure Au130(p-MBT)50, Au104(m-MBT)41 and Au40(o-MBT)24 nanoclusters. The decreasing size sequence is in line with the increasing hindrance of the methyl group to the interfacial Au-S bond. That the subtle change of ligand structure can result in drastically different magic sizes under otherwise similar reaction conditions is indeed for the first time observed in the synthesis of thiolate-protected gold nanoclusters. These nanoclusters are highly stable as they are synthesized under harsh size-focusing conditions at 80-90 °C in the presence of excess thiol and air (i.e., without exclusion of oxygen).

Decorated carbon nanotubes with unique oxygen sensitivity

The relatively simple and robust architecture of microelectronic devices based on carbon nanotubes, in conjunction with their environmental sensitivity, places them among the leading candidates for incorporation into ultraportable or wearable chemical analysis platforms. We used single-walled carbon nanotube (SWNT) networks to establish a mechanistic understanding of the solid-state oxygen sensitivity of a Eu(3+)-containing dendrimer complex. After illumination with 365 nm light, the SWNT networks decorated with the Eu(3+) dendrimer show bimodal (optical spectroscopic and electrical conductance) sensitivity towards oxygen gas at room temperature under ambient pressure. We investigated the mechanism of this unique oxygen sensitivity with time-resolved and steady-state optical spectroscopy, analysis of excited-state luminescence lifetimes and solid-state electrical transport measurements. We demonstrate a potential application of this system by showing a reversible and linear electrical response to oxygen gas in the tested range (5-27%).

Efficient electrochemical CO2 conversion powered by renewable energy

The catalytic conversion of CO2 into industrially relevant chemicals is one strategy for mitigating greenhouse gas emissions. Along these lines, electrochemical CO2 conversion technologies are attractive because they can operate with high reaction rates at ambient conditions. However, electrochemical systems require electricity, and CO2 conversion processes must integrate with carbon-free, renewable-energy sources to be viable on larger scales. We utilize Au25 nanoclusters as renewably powered CO2 conversion electrocatalysts with CO2 → CO reaction rates between 400 and 800 L of CO2 per gram of catalytic metal per hour and product selectivities between 80 and 95%. These performance metrics correspond to conversion rates approaching 0.8-1.6 kg of CO2 per gram of catalytic metal per hour. We also present data showing CO2 conversion rates and product selectivity strongly depend on catalyst loading. Optimized systems demonstrate stable operation and reaction turnover numbers (TONs) approaching 6 × 10(6) molCO2 molcatalyst(-1) during a multiday (36 h total hours) CO2 electrolysis experiment containing multiple start/stop cycles. TONs between 1 × 10(6) and 4 × 10(6) molCO2 molcatalyst(-1) were obtained when our system was powered by consumer-grade renewable-energy sources. Daytime photovoltaic-powered CO2 conversion was demonstrated for 12 h and we mimicked low-light or nighttime operation for 24 h with a solar-rechargeable battery. This proof-of-principle study provides some of the initial performance data necessary for assessing the scalability and technical viability of electrochemical CO2 conversion technologies. Specifically, we show the following: (1) all electrochemical CO2 conversion systems will produce a net increase in CO2 emissions if they do not integrate with renewable-energy sources, (2) catalyst loading vs activity trends can be used to tune process rates and product distributions, and (3) state-of-the-art renewable-energy technologies are sufficient to power larger-scale, tonne per day CO2 conversion systems.

Photomediated Oxidation of Atomically Precise Au25(SC2H4Ph)18(-) Nanoclusters.

The anionic charge of atomically precise Au25(SC2H4Ph)18(-) nanoclusters (abbreviated as Au25(-)) is thought to facilitate the adsorption and activation of molecular species. We used optical spectroscopy, nonaqueous electrochemistry, and density functional theory to study the interaction between Au25(-) and O2. Surprisingly, the oxidation of Au25(-) by O2 was not a spontaneous process. Rather, Au25(-)-O2 charge transfer was found to be a photomediated process dependent on the relative energies of the Au25(-) LUMO and the O2 electron-accepting level. Photomediated charge transfer was not restricted to one particular electron accepting molecule or solvent system, and this phenomenon likely extends to other Au25(-)-adsorbate systems with appropriate electron donor-acceptor energy levels. These findings underscore the significant and sometimes overlooked way that photophysical processes can influence the chemistry of ligand-protected clusters. In a broader sense, the identification of photochemical pathways may help develop new cluster-adsorbate models and expand the range of catalytic reactions available to these materials.

Probing active site chemistry with differently charged Au25q nanoclusters (q = −1, 0, +1)

Charged active sites are hypothesized to participate in heterogeneously-catalyzed reactions. For example, Auδ+ species at the catalyst surface or catalyst–support interface are thought to promote the thermally-driven CO oxidation reaction. However, the concept of charged active sites is rarely extended to electrochemical systems. We used atomically precise Au25q nanoclusters with different ground state charges (q = −1, 0, +1) to study the role of charged active sites in Au-catalyzed electrochemical reactions. Au25q clusters showed charge state-dependent electrocatalytic activity for CO2 reduction, CO oxidation and O2 reduction reactions in aqueous media. Experimental studies and density functional theory identified a relationship between the Au25q charge state, the stability of adsorbed reactants or products, and the catalytic reaction rate. Anionic Au25− promoted CO2 reduction by stabilizing coadsorbed CO2 and H+ reactants. Cationic Au25+ promoted CO oxidation by stabilizing coadsorbed CO and OH− reactants. Finally, stronger product adsorption at Au25+ inhibited O2 reduction rates. The participation of H+ and OH− in numerous aqueous electrocatalytic reactions likely extends the concept of charge state-mediated reactivity to a wide range of applications, including fuel cells, water splitting, batteries, and sensors. Au25q clusters have also shown photocatalytic and more traditional thermocatalytic activity, and the concept of charge state-mediated reactivity may create new opportunities for tuning reactant, intermediate and product interactions in catalytic systems extending beyond the field of electrochemistry.

Synthesis of ultrasmall platinum nanoparticles and structural relaxation

We report the synthesis of ligand-protected, ultrasmall Pt nanoparticles of ∼1 nm size via a one-phase wet chemical method. Using matrix-assisted laser desorption ionization mass spectrometry (MALDI-MS), we determined the mass of the nanoparticles to be ∼8 kDa. Characterization of the Pt nanoparticles was further carried out by powder X-ray diffraction (XRD), transmission electron microscopy (TEM), thermogravimetric analysis (TGA), optical absorption spectroscopy, and X-ray photoelectron spectroscopy (XPS). Interestingly, we observed a large structural relaxation in the 8kDa nanoparticles (i.e. lattice parameter elongation by +10%) compared to bulk platinum. XPS analysis revealed a positive shift of Pt 4f core level energy by approximately +1 eV compared with bulk Pt, indicating charge transfer from Pt to S atom of the thiolate ligand on the particle. Compared to bulk Pt, the 5d band of Pt nanoparticles is narrower and shifts to higher binding energy. Overall, the ∼1 nm ultrasmall Pt nanoparticles exhibit quite distinct differences in electronic and structural properties compared to their larger counterparts and bulk Pt.