Electronic Tuning of Gold Nanoparticle Active Sites for Reduction Catalysis.

Electronic tuning of active sites in heterogeneous catalysis with organic ligands remains challenging since the ligands are often bound to the most active sites on the catalysts' surfaces. In this work, gold nanoparticles, which are on average less than 2 nm in diameter, are synthesized with strongly binding thiol and phosphine ligands and have measurable quantities of accessible sites on their surfaces in both cases. Triphenylphosphine (TPP) is used as the phosphine ligand, while triphenylmethyl mercaptan (TPMT) serves as the thiol ligand. Phosphines are chosen because they are electron-donating ligands when bound to Au, and thiols are selected because they are electron-withdrawing on the Au surface. X-ray photoelectron spectroscopy (XPS) results show differences in the Au 4f binding energies between the TPP- and TPMT-bound Au nanoparticles. Fourier transform infrared spectroscopy (FTIR) measurements of bound CO indicate that the TPP-bound Au nanoparticles are more electron-rich than the TPMT-bound Au nanoparticles. The number of binding sites on the surface is quantified using 2-naphthalenethiol titration experiments. It is observed that the number of binding sites on the thiol and phosphine-bound Au nanoparticles is similar in both cases. The Au nanoparticles are used for three different reactions: resazurin reduction, CO oxidation, and benzyl alcohol oxidation. For both CO oxidation and benzyl alcohol oxidation, which are performed with the ligands attached, TPP- and TPMT-bound nanoparticles are both catalytically active. However, for resazurin reduction, the TPMT-bound Au nanoparticles are not active, while the TPP-bound Au nanoparticles are catalytically active. These results illustrate that the catalytic activity can be tuned using bound organic ligands with different electronic properties for reduction reactions using Au nanoparticle catalysts.

Catalytic ammonia reforming: alternative routes to net-zero-carbon hydrogen and fuel.

Ammonia is an energy-dense liquid hydrogen carrier and fuel whose accessible dissociation chemistries offer promising alternatives to hydrogen electrolysis, compression and dispensing at scale. Catalytic ammonia reforming has thus emerged as an area of renewed focus within the ammonia and hydrogen energy research & development communities. However, a majority of studies emphasize the discovery of new catalytic materials and their evaluation under idealized laboratory conditions. This Perspective highlights recent advances in ammonia reforming catalysts and their demonstrations in realistic application scenarios. Key knowledge gaps and technical needs for real reformer devices are emphasized and presented alongside enabling catalyst and reaction engineering fundamentals to spur future investigations into catalytic ammonia reforming.

Synthesis of Highly Accessible and Reactive Sites in Gold Nanoparticles Using Bound Bis(Diphenylphosphine) Ligands.

While bound organic ligands provide steric protection against aggregation for metallic nanoparticles in solution, they can block a large fraction of the surface atoms which are needed for binding in catalysis and sensing applications. In this work, highly accessible Au nanoparticles ligated with bis(diphenylphosphine) molecules are synthesized and characterized in solution. Characterization is performed using high angle annular dark field-scanning transmission electron microscopy (HAADF-STEM), ultraviolet-visible (UV-Vis) spectroscopy, and fluorescence chemisorption experiments. These synthesized nanoparticles are accessible to a 2-napthalenethiol (2-NT) probe molecule in solution. The highest 2-NT accessibility is observed when using 1,1-bis(diphenylphosphino)methane (dppm) ligand where 61 % of the total gold atoms are accessible. It is hypothesized that increasing the rigidity of the bis(diphenylphosphine) ligand increases the number of binding sites on the Au nanoparticles. These nanoparticles are catalytically active for resazurin reduction, and the resazurin reduction rate scales with the number of binding sites.

Gold nanoparticles with tailored size through ligand modification for catalytic applications.

The active sites of catalysts can be tuned by using appropriate organic moieties. Here, we describe a facile approach to synthesise gold nanoparticles (AuNPs) using various Au(I) precursors. The core size of these AuNPs can be precisely tailored by varying the steric hindrance imposed by bound ligands. An interesting relationship is deduced that correlates the steric hindrance around the metal to the final size of the nanoparticles. The synthesised AuNPs are immobilised onto TS-1 zeolite (Au/TS-1) with minimal change in the final size of the AuNPs. The catalytic performance of Au/TS-1 catalyst is evaluated for the direct gas phase epoxidation of propylene with hydrogen and oxygen, an environmentally friendly route to produce propylene oxide. The results indicate that smaller AuNPs exhibit enhanced catalytic activity and selectivity. Furthermore, this synthetic approach is beneficial when tailored synthesis of gold nanoparticles of specific sizes is required.

Compensation Effect Exhibited by Gold Bimetallic Nanoparticles during CO Oxidation.

While CO oxidation catalyzed by gold nanoparticles has been practiced academically for several decades, there are still important discoveries to be made. One area of current interest is to pair Au with another alloying metal and observe the catalytic consequences of the presence of the other metal. In this work, TiO2-supported bimetallic Au nanoparticles are alloyed with Cu, Co, Ni, Pd, and Ru and used as catalysts for CO oxidation. Two synthetic methods for the alloys are presented: a strong electrostatic adsorption (SEA) method and a sterically demanding ligand synthesis (SDLS) method which uses triphenylphosphine (TPP) as the ligand. The catalytic performance of the materials synthesized with the SEA and SDLS methods is compared in CO oxidation. The results indicate that the materials tested present an enthalpy-entropy compensation effect. Interestingly, both the enthalpy of activation, ΔH ‡, and the entropy of activation, ΔS ‡, generally decrease with particle size. AuCo and AuRu materials exhibit a decrease in the overall activity as compared to Au and the other Au alloys when synthesized via SEA. Au face-centered-cubic alloys AuCu, AuNi, and AuPd prepared via SEA show an improvement in activity compared to monometallic Au in our reaction conditions. In situ diffuse reflectance infrared Fourier transform spectroscopy presents two distinct regions for Au bimetallics where AuCo and AuRu show peak positions in the region of 2070-2050 cm-1, indicating a weaker interaction for AuCo and AuRu with CO when compared to that of the other alloys. For the SDLS method samples, the hypothesis is that TPP would enhance the CO oxidation rate by enhancing the charge transfer to the metallic surface. The results indicate that SDLS samples have lower CO oxidation rates and if any charge transfer occurs, it is masked by the lateral interactions of the CO π bonds and the phenyl groups of TPP.

Precisely Engineered Supported Gold Clusters as a Stable Catalyst for Propylene Epoxidation.

Designing a stable and selective catalyst with high H2 utilisation is of pivotal importance for the direct gas-phase epoxidation of propylene. This work describes a facile one-pot methodology to synthesise ligand-stabilised sub-nanometre gold clusters immobilised onto a zeolitic support (TS-1) to engineer a stable Au/TS-1 catalyst. A non-thermal O2 plasma technique is used for the quick removal of ligands with limited increase in particle size. Compared to untreated Au/TS-1 catalysts prepared using the deposition precipitation method, the synthesised catalyst exhibits improved catalytic performance, including 10 times longer lifetime (>20 days), increased PO selectivity and hydrogen efficiency in direct gas phase epoxidation. The structure-stability relationship of the catalyst is illustrated using multiple characterisation techniques, such as XPS, 31 P MAS NMR, DR-UV/VIS, HRTEM and TGA. It is hypothesised that the ligands play a guardian role in stabilising the Au particle size, which is vital in this reaction. This strategy is a promising approach towards designing a more stable heterogeneous catalyst.

Plasmonic Photocatalytic Enhancement of L-Cysteine Self-Assembled Gold Nanoparticle Clusters for Fenton Reaction Catalysis.

Plasmon-enhanced photocatalysis has the potential to reduce activation energies and decrease temperature requirements, which increases catalyst stability and lowers process operating costs. The near-field enhancement that occurs at junctions between plasmonic nanoparticle clusters (i.e., hot spots) has been well-studied for sensing applications (e.g., Raman scattering). However, experimental insight into the effect of nanoparticle cluster hot spots on plasmon-enhanced photocatalysis is lacking. We demonstrate that catalytic activity is increased when clusters of gold nanoparticles (AuNPs) are formed relative to isolated particles using the same catalyst loading. Through experimental controls, we conclude that this catalytic enhancement is most likely due to the formation of plasmonic hot spots. Clusters of AuNPs were formed by adding L-cysteine to an AuNP dispersion, and a 20 ± 12% enhancement in the photocatalytic dye degradation rate was observed using a Fenton process. While this report may be a modest enhancement relative to the spectacular near-field electromagnetic field enhancements predicted by simulation at the nanoparticle junction, this finding supports the recent work of Srimanta et al. that plasmonic hot spots contribute to catalytic rate enchantments. It is anticipated that further self-assembly strategies to optimize interparticle orientations and cluster size distributions will improve the enhancement due to the formation of hot spots, and careful control will be required. For example, excess L-cysteine addition revealed extensive aggregation and subsequent rate reductions.

Mesostructure of Mesoporous Silica/Anodic Alumina Hierarchical Membranes Tuned with Ethanol.

Hierarchically structured membranes composed of mesoporous silica embedded inside the channels of anodic alumina (MS-AAM) were synthesized using the aspiration method. Ethanol is shown to have a significant effect on the type and organization of the mesoporous silica phase. Detailed textural analysis revealed that the pore size distribution of the mesoporous silica narrows and the degree of ordering increases with decreasing ethanol concentration used in the synthesis mixture. The silica mesopores were synthesized with pores as small as 6 nm in diameter, with the channel direction oriented in lamellar, circular, and columnar directions depending on the ethanol content. This study reveals ethanol concentration as a key factor behind the synthesis of an ordered mesoporous silica-anodic alumina membrane that can increase its functionality for membrane-based applications.

Accessible gold clusters using calix[4]arene N-heterocyclic carbene and phosphine ligands.

We investigate the synthesis of accessible calix[4]arene-bound gold clusters consisting of open "coordinatively unsaturated" active sites, using a comparative approach that relies on calix[4]arene ligands with various upper- and lower-rim substituents. In contrast with a reported Au(I)-tert-butyl-calixarene phosphine complex, which exhibits a single cone conformer in solution, the H upper-rim analog exhibits multiple conformers in solution. This contrasts with observations of the tert-butyl upper-rim analog, which exhibits a single cone conformer in solution under similar conditions. In the solid state, as determined by single-crystal X-ray diffraction, both H and tert-butyl upper-rim analogs exhibit exclusively cone conformer. A detailed structural analysis of these two solid-state structures highlights a CH-π interaction involving a methoxy lower-rim substituent and phenyl substituent on P as the key feature that enforces a tight configuration of Au(I) atoms on the same side of the calix[4]arene lower-rim plane. We hypothesize that such a configuration promotes chelation of the ligand to a gold surface and facilitates the synthesis of small Au11-sized clusters after reduction of both complexes. The new cluster, like the one reported with the tert-butyl analog, has an extraordinary 25% of surface atoms that are open and accessible to a 2-NT (2-naphthalenethiol) probe in solution. We also investigated the effect of calix[4]arene lower-rim substituents that coordinate to the metal, by using N-heterocyclic carbene (NHC) functional groups rather than phosphines. Four small (<1.6 nm diameter) calix[4]arene NHC-bound gold clusters were synthesized, including three using novel calix[4]arene NHC ligands. The smallest calix[4]arene NHC-bound Au cluster consisted of a 1.2 nm gold core, and its number density of accessible and open surface sites was measured. This required development of a new titration method for open sites on gold clusters, using a SAMSA fluorescein dye molecule, which excites and emits at lower energy relative to the previously used 2-NT probe. The number density of open sites on the new calix[4]arene NHC-bound gold cluster measured by the SAMSA fluorescein probe strongly supports the generality of a mechanical model of accessibility, which does not depend on the functional group involved in binding to the gold surface and rather depends on the relative radii of curvature of bound ligands and the gold cluster core.

Delamination of layered zeolite precursors under mild conditions: synthesis of UCB-1 via fluoride/chloride anion-promoted exfoliation.

New material UCB-1 is synthesized via the delamination of zeolite precursor MCM-22 (P) at pH 9 using an aqueous solution of cetyltrimethylammonium bromide, tetrabutylammonium fluoride, and tetrabutylammonium chloride at 353 K. Characterization by powder X-ray diffraction, transmission electron microscopy, and nitrogen physisorption at 77 K indicates the same degree of delamination in UCB-1 as previously reported for delaminated zeolite precursors, which require a pH of greater than 13.5 and sonication in order to achieve exfoliation. UCB-1 consists of a high degree of structural integrity via (29)Si MAS NMR and Fourier transform infrared spectroscopies, and no detectable formation of amorphous silica phase via transmission electron microscopy. Porosimetry measurements demonstrate a lack of hysteresis in the N(2) adsorption/desorption isotherms and macroporosity in UCB-1. The new method is generalizable to a variety of Si:Al ratios and leads to delaminated zeolite precursor materials lacking amorphization.

A bioinspired approach for controlling accessibility in calix[4]arene-bound metal cluster catalysts.

In enzymes, the electronic and steric environments of active centres, and therefore their activity in biological processes, are controlled by the surrounding amino acids. In a similar manner, organic ligands have been used for the 'passivation' of metal clusters, that is, inhibition of their aggregation and control of their environment. However, the ability of enzymes to maintain large degrees of accessibility has remained difficult to mimic in synthetic systems in which little room, if any, is typically left to bind to other species. Here, using calix[4]arene macrocycles bearing phosphines as crude mimics of the rigid backbones of proteins, we demonstrate the synthesis of gold clusters and the control of their accessibility through an interplay between the sizes of the calixarene ligands and metal cores. For 0.9-nm cores, 25% of all the gold atoms within the cluster bind to the chemisorption probe 2-naphthalenethiol. This accessibility dramatically decreases with 1.1-nm and 4-nm gold cores.

Synthesis of CdSe quantum dots with luminescence in the violet region of the solar spectrum.

We have designed a simple, one-step synthesis of CdSe quantum dots with photoluminescence frequencies ranging from the red through to the violet region of the solar spectrum. The photoluminescence peaks have FWHM of 30 nm indicating absorption over a narrow range of wavelengths. The effect of solvent type and solvent boiling point on the physical and photoluminescence properties of the quantum dots has been studied. High boiling point, non-polar solvents shift the photoluminescence peak to longer wavelengths and low boiling point, polar solvents shift the photoluminescence peak to shorter wavelengths.