The Effectiveness of Silver and Gold in Catalytic Homogenous and Heterogenous Borohydride Hydrolysis - a DFT Study.

Energy demands, and environmental aspects raised the need to study hydrogen-carrying material such as borohydride for the practical usage of hydrogen as a cleaner and more efficient fuel. A proper understanding of the hydrogen generation mechanism is a key requirement for the designing of efficient catalysts, as the non-catalytic hydrolysis of borohydride in non-acidic media is a slow process. The hydrolysis mechanism of borohydride varies considerably using homogeneous and heterogeneous catalysts. A comparison of the hydrolysis mechanism of borohydride using gold and silver as homogenous and heterogeneous catalysts is given in this review. Unexpectedly, with gold catalyst, Au+ or Au(111), only two steps of hydrolysis occur and BH(OH)2 is produced, while with silver catalyst, Ag+ or Ag(111), the hydrolysis can proceed to completion.

Hydrogen adsorption on various transition metal (111) surfaces in water: a DFT forecast.

The hydrogen adsorption and hydrogen evolution at the M(111), (M = Ag, Au Cu, Pt, Pd, Ni & Co) surfaces of various transition metals in aqueous suspensions were studied computationally using the DFT methods. The hydrogens are adsorbed dissociatively on all surfaces except on Ag(111) and Au(111) surfaces. The results are validated by reported experimental and computational studies. Hydrogen atoms have large mobility on M(111) surfaces due to the small energy barriers for diffusion on the surface. The hydrogen evolution via the Tafel mechanism is considered at different surface coverage ratios of hydrogen atoms and is used as a descriptor for the hydrogen adsorption capacity on M(111) surfaces. All calculations are performed without considering how the hydrogen atoms are formed on the surface. The hydrogen adsorption energies decrease with the increase in the surface coverage of hydrogen atoms. The surface coverage for the H2 evolution depends on each M(111) surface. Among the considered M(111) surfaces, Au(111) has the least hydrogen adsorption capacity and Ni, Co and Pd have the highest. Furthermore, experiments proving that after the H2 evolution reaction (HER) on Au0-NPs, and Ag0-NPs surfaces some reducing capacity remains on the M0-NPs is presented.

On The Nature of FeIV =Oaq in Aqueous Media: A DFT analysis.

FeIV =Oaq is a key intermediate in many advanced oxidation processes and probably in biological systems. It is usually referred to as FeIV =O2+ . The pKa's of FeIV =Oaq as derived by DFT are: pKa1=2.37 M06 L/6-311++G(d,p) (SDD for Fe) and pKa2=7.79 M06 L/6-311++G(d,p) (SDD for Fe). This means that in neutral solutions, FeIV =Oaq is a mixture of (H2 O)4 (OH)FeIV =O+ and (H2 O)2 (OH)2 FeIV =O. The oxidation potential of FeIV =Oaq in an acidic solution, E0 {(H2 O)5 FeIV =O2+ /FeIII (H2 O)6 3+ , pH 0.0} is calculated with and without a second solvation sphere and the recommended value is between 2.86 V (B3LYP/Def2-TZVP, with a second solvation sphere) and 2.23 V (M06 L/Def2-TZVP without a second solvation sphere). This means that FeIV =Oaq is the strongest oxidizing agent formed in systems involving FeVI O4 2- even in neutral media.

Dual Role of Silicon-based Matrices in Electron Exchange Matrices for Waste Treatment.

Para chloro aniline (PCA) is a common toxic pollutant found in pharmaceutical wastewater. Our study suggests a novel PCA treatment method based on a heterogeneous advanced oxidation process (AOP) that proceeds in an electron exchange matrix (EEM) prepared by the incorporation of redox-active specie in silica matrices using the sol-gel synthesis route. The results, which are supported by DFT calculations, show that the silicon skeleton of the EEM has two important roles, both as a porous matrix that hosts the redox species and as an oxidant species involved in the AOP. The calculations indicate that the formation of a radical on the nitrogen is favored. The suggested mechanism could shed light on the AOP, which proceeds in a heterogenous system, and on its application inside the understudied EEMs that, until now, have been a virtual black box. A better understanding of the mechanism could lead to improved control over the heterogeneous processes that can play a critical role in industries with the need to treat small amounts of toxic compounds at low concentrations, such as in the pharmaceutical industry.

DFT Study of the BH4 - Hydrolysis on Au(111) Surface.

The mechanism of the catalytic hydrolysis of BH4 - on Au(111) as studied by DFT is reported. The results are compared to the analogous process on Ag(111) that was recently reported. It is found that the borohydride species are adsorbed stronger on the Au0 -NP surface than on the Ag0 -NP surface. The electron affinity of the Au is larger than that of Ag. The results indicate that only two steps of hydrolysis are happening on the Au(111) surface and the reaction mechanism differs significantly from that on the Ag(111) surface. These remarkable results were experimentally verified. Upon hydrolysis, only three hydrogens of BH4 - are transferred to the Au surface, not all four, and H2 generation is enhanced in the presence of surface H atoms. Thus, it is proposed that the BH4 - hydrolysis and reduction mechanisms catalyzed by M0 -NPs depend considerably on the nature of the metal.

Calculating the adsorption energy of a charged adsorbent in a periodic metallic system - the case of BH4- hydrolysis on the Ag(111) surface.

The hydrolysis of borohydride on the Ag(111) surface is explored theoretically to obtain the in-depth reaction mechanism. Many heterogeneously catalyzed reactions like this involve the adsorption of charged species on metals. DFT calculations of charged systems, with periodic boundaries, face serious problems, concerning convergence and reliability of the results. To study the heterogeneously catalyzed reactions, a simple method to calculate the adsorption energy of charged systems in metallic periodic cells is proposed. In this method, a counter ion is placed at a non-interactive distance, in an aqueous medium, so that the calculated system is neutral. Bader analysis is used to validate that the calculated couple is charged correctly. Adsorption energies of F-, Cl-, Br-, OH-, BH4-, ClO4- and H- ions on the Ag(111) surface in an aqueous medium were determined using Na+ and K+ as counter ions, to evaluate the performance of this method. The adsorption of the divalent ions S2-, Se2- and SO42- on different surfaces was studied as well. Then this method was used to explore the hydrolysis of BH4- ions, which have a high theoretical hydrogen storage capacity, on the Ag(111) surface. The results point out that during the catalytic hydrolysis only one hydrogen atom from borohydride is transferred to the surface. In the first step one hydrogen atom from BH4- is transferred to the silver surface; this H atom reacts with a hydrogen atom that is released from an adsorbed water molecule; in addition, a hydrogen molecule is released in the second step (one atom from *BH4- and one from *H2O). Thus, the mechanisms of the catalyzed reductions by BH4- and the hydrogen evolution reactions must be reconsidered.

Mechanism of Producing Metallic Nanoparticles, with an Emphasis on Silver and Gold Nanoparticles, Using Bottom-Up Methods.

Bottom-up nanoparticle (NP) formation is assumed to begin with the reduction of the precursor metallic ions to form zero-valent atoms. Studies in which this assumption was made are reviewed. The standard reduction potential for the formation of aqueous metallic atoms-E0(Mn+aq/M0aq)-is significantly lower than the usual standard reduction potential for reducing metallic ions Mn+ in aqueous solution to a metal in solid state. E0(Mn+aq/M0solid). E0(Mn+aq/M0aq) values are negative for many typical metals, including Ag and Au, for which E0(Mn+aq/M0solid) is positive. Therefore, many common moderate reduction agents that do not have significantly high negative reduction standard potentials (e.g., hydrogen, carbon monoxide, citrate, hydroxylamine, formaldehyde, ascorbate, squartic acid, and BH4-), and cannot reduce the metallic cations to zero-valent atoms, indicating that the mechanism of NP production should be reconsidered. Both AgNP and AuNP formations were found to be multi-step processes that begin with the formation of clusters constructed from a skeleton of M+-M+ (M = Ag or Au) bonds that is followed by the reduction of a cation M+ in the cluster to M0, to form Mn0 via the formation of NPs. The plausibility of M+-M+ formation is reviewed. Studies that suggest a revised mechanism for the formation of AgNPs and AuNPs are also reviewed.

On the Differences in the Mechanisms of Reduction of AuCl2- and Ag(H2O)2+ with BH4.

The mechanism of reduction of AuCl4-/AuCl3OH- by BH4- was analyzed by density functional theory (DFT). The results point out that Auatoms0 are not intermediates in the process. The derived mechanism differs considerably from that reported for the analogous process involving the reduction of Ag(H2O)2+ by BH4-. Thus, though both processes follow the Creighton procedure, the detailed mechanism differs significantly. For Au, the agglomeration starts with AuH2-, whereas for Ag, it starts with (H2O)AgH. Stopped-flow measurements support the complicated mechanism.

Mechanistic Studies on the Role of [CuII (CO3 )n ]2-2n as a Water Oxidation Catalyst: Carbonate as a Non-Innocent Ligand.

Recently it was reported that copper bicarbonate/carbonate complexes are good electro-catalysts for water oxidation. However, the results did not enable a decision whether the active oxidant is a CuIII or a CuIV complex. Kinetic analysis of pulse radiolysis measurements coupled with DFT calculations point out that CuIII (CO3 )n3-2n complexes are the active intermediates in the electrolysis of CuII (CO3 )n2-2n solution. The results enable the evaluation of E°[(CuIII/II (CO3 )n )aq ]≈1.42 V versus NHE at pH 8.4. This redox potential is in accord with the electrochemical report. As opposed to literature suggestions for water oxidation, the present results rule out single-electron transfer from CuIII (CO3 )n3-2n to yield hydroxyl radicals. Significant charge transfer from the coordinated carbonate to CuIII results in the formation of C2 O62- by means of a second-order reaction of CuIII (CO3 )n3-2n . The results point out that carbonate stabilizes transition-metal cations at high oxidation states, not only as a good sigma donor, but also as a non-innocent ligand.

Carbonate and carbonate anion radicals in aqueous solutions exist as CO3(H2O)62- and CO3(H2O)6˙- respectively: the crucial role of the inner hydration sphere of anions in explaining their properties.

An effort to reproduce the chemical and physical properties of carbonate and carbonate anion radicals in aqueous solutions by DFT proves that one has to include an inner hydration sphere of six water molecules for both anions. Application of the SMD model to CO3(H2O)62- and CO3(H2O)6˙- enables achievement of the experimental value of the redox potential of the CO3(H2O)6˙-/2- couple. This is a result of the direct inclusion of a considerable charge transfer (CT) from CO32- to its inner hydration sphere in the calculation of the hydration effect. The HOMO of clusters is an analogue of the non-bonding σ-type a2'-HOMO of the parent CO3 moiety with a σ*(OH) contribution. This is a MO manifestation of the CT to the first hydration shell. The localization of the CT on the first hydration shell also re-produces the very strong OHO stretch peak. Furthermore, the very large difference in the hydration energies of CO32- and CO3˙- which causes the very large differences in the length of the C-OH-O hydrogen bonds suggests that the oxidations by CO3˙- proceed via the inner sphere mechanism.

The plausible role of carbonate in photo-catalytic water oxidation processes.

DFT calculations point out that the photo-oxidation of water on GaN is energetically considerably facilitated by adsorbed carbonate. As the redox potential of the couple CO3(˙-)/CO3(2-) is considerably lower than that of the couple OH˙/OH(-) but still enables the oxidation of water it is suggested that carbonate should be considered as a catalyst/co-catalyst in a variety of catalytic/photo-catalytic/electro-catalytic oxidation processes.

Plausible mechanisms of the fenton-like reactions, M = Fe(II) and Co(II), in the presence of RCO2(-) substrates: are OH(•) radicals formed in the process?

DFT calculations concerning the plausible mechanism of Fenton-like reactions catalyzed by Fe(II) and Co(II) cations in the presence of carboxylate ligands suggest that hydroxyl radicals are not formed in these reactions. This conclusion suggests that the commonly accepted mechanisms of Fenton-like reactions induced oxidative stress and advanced oxidation processes have to be reconsidered.

Development of Meta-Chemical Surface by Dip-Pen Nanolithography for Precise Electrochemical Lead Sensing.

Dip-pen nanolithography (DPN) is a powerful and unique technique for precisely depositing tiny nano-spherical cap shapes (nanoclusters) onto a desired surface. In this study, a meta-chemical surface (MCS; a pattern with advanced features) is developed by DPN and applied to electrochemical lead sensing, yielding a calibration curve in the ppb range. An ink mixture of PMMA and NTPH (which binds to Pb (II), as supported by DFT calculations) is patterned over a Pt surface. The average height of the nanoclusters is ≈13 nm with a high surface area-to-volume ratio, which depends on the ink composition and the MCS surface. This ratio affected the sensitivity of the MCS as a detecting tool. The results indicate that the sensor's features can be controlled by the ability to control the size of the nanoclusters, attributed to the unique properties of the DPN production method. These results are significant for the water-source purification industry.

Chemical-Dealloying-Derived PtPdPb-Based Multimetallic Nanoparticles: Dimethyl Ether Electrocatalysis and Fuel Cell Application.

In this work, we report a novel multimetallic nanoparticle catalyst composed of Pt, Pd, and Pb and its electrochemical activity toward dimethyl ether (DME) oxidation in liquid electrolyte and polymer electrolyte fuel cells. Chemical dealloying of the catalyst with the lowest platinum-group metal (PGM) content, Pt2PdPb2/C, was conducted using HNO3 to tune the catalyst activity. Comprehensive characterization of the chemical-dealloying-derived catalyst nanoparticles unambiguously showed that the acid treatment removed 50% Pb from the nanoparticles with an insignificant effect on the PGM metals and led to the formation of smaller-sized nanoparticles. Electrochemical studies showed that Pb dissolution led to structural changes in the original catalysts. Chemical-dealloying-derived catalyst nanoparticles made of multiple phases (Pt, Pt3Pb, PtPb) provided one of the highest PGM-normalized power densities of 118 mW mgPGM-1 in a single direct DME fuel cell operated at low anode catalyst loading (1 mgPGM cm-2) at 70 °C. A possible DME oxidation pathway for these multimetallic catalysts was proposed based on an online mass spectrometry study and the analysis of the reaction products.

Elucidation of a mechanism for the heterogeneous electro-fenton process and its application in the green treatment of azo dyes.

Vast efforts are directed today toward the development of efficient, green methods for the degradation of toxic compounds, especially those that are water-soluble. Though Fenton reactions are commonly used in wastewater treatment, their mechanisms and the active species involved remain obscure due to their mechanistic complexity. In this work, the mechanism of an electro-Fenton reaction, in which a FeLaO3 catalyst was entrapped in a sol-gel matrix, was studied in the presence of azo dyes as the model for toxic compounds. Increased knowledge about this important mechanism will confer greater control over related processes and enable a more efficient and green degradation method. DFT calculations showed that in the presence of Fe(IV), OH are formed under acidic conditions and that both the iron and hydroxyl species function as oxidation reagents in the degradation process. The structure of the formed Fe(IV) embedded in the solid matrix was not the typical tetravalent structure. Entrapment in the sol-gel matrix stabilized the catalyst, enhanced its efficiency and enabled it to be recycled. Sol-gel matrices constitute a simple method for the degradation of stable and toxic compounds under extreme pH conditions. The findings of this study are highly significant for the treatment of typically acidic wastewaters.

On the reactions of Cu(II/I)ATP complexes with methyl radicals.

The CuI/IIATP react with methyl radicals to form methane and methanol, where CuIATP reacts with •CH3 in a process that is surprisingly slow. The low-rate constant of this process is attributed to the significant rearrangement of the chelating ligand required for the transient's formation. These results were corroborated by DFT calculations of the relevant compounds.

Enhancing the catalytic OER performance of MoS2via Fe and Co doping.

Enhancing the sluggish kinetics of the electrochemical oxygen evolution reaction (OER) is crucial for many clean-energy production technologies. Although much progress has been made in recent years, developing active, stable, and cost-effective OER electrocatalysts is still challenging. The layered MoS2, based on Earth-abundant elements, is widely explored as a promising hydrogen evolution electrocatalyst but exhibits poor OER activity. Here, we report a facile strategy to improve the sluggish OER of MoS2 through co-doping MoS2 nanosheets with Fe and Co atoms. The synergistic effect obtained by adjusting the Co/Fe ratio in the Fe-Co doped MoS2 induces electronic and structural modifications and a richer active surface area morphology resulting in a relatively low OER overpotential of 380 mV (at 10 mA cm-2). The electronic modulation upon doping was further supported by DFT calculations that show favorable interaction with the OER intermediate species, thus reducing the energy barrier for the OER. This work paves the way for future strategies for tailoring the electronic properties of transition-metal dichalcogenides (TMDCs) to activate the structure for the sluggish OER with the assistance of non-noble-metal materials.

Sonication-Induced, Solvent-Selective Gelation of a 1,8-Napthalimide-Conjugated Amide: Structural Insights and Pollutant Removal Applications.

Reported herein is the synthesis, characterization, and dye removal applications of a highly solvent-selective organogel-forming amide, compound 1, which contains a 1,8-naphthalmide moiety, flexible n-hexyl chain, and benzene ring. This compound displayed remarkable solvent selectivity, with gel formation occurring only in the presence of alkylated aromatic solvents. Detailed structural characterization of the gels, combined with notable theoretical insights, is invoked to explain the highly selective gelation properties of compound 1, as is a comparison to non-gel forming structural isomer 2, which contains the same structural elements in a different arrangement. Finally, the ability of the gel derived from compound 1 to act as a reusable material for the efficient removal of cationic organic dyes from contaminated aqueous environments is also reported, with up to 11 repeated uses of the gel still maintaining the ability to effectively remove Rhodamine B.

Radicals in 'biologically relevant' concentrations behave differently: Uncovering new radical reactions following the reaction of hydroxyl radicals with DMSO.

Methyl radicals play key roles in various chemical and biological processes. Mechanistic studies of methyl radicals with their precursor, Dimethyl Sulfoxide (DMSO), were extensively studied. Though the involved mechanisms seemed to be clarified, essentially none of the studies have been performed at conditions relevant to both biological and catalytic systems, i.e. low steady state radical concentrations. A chain-like reaction, as an inverse function of the radicals concentrations ([•CH3]ss), increases the methyl radical yields. The nature of the additional products obtained differs from those commonly observed. Furthermore it is shown that methyl radicals abstract a methyl group from DMSO to yield ethane. Herein we report a novel mechanism relevant mainly at low steady state radical concentrations, which may change the understanding of certain reaction routes present in both biological systems and catalytic chemical systems. Thus the results point out that mechanistic studies have to be carried out at dose rates forming radicals at analogous concentrations to those present in the process of interest.

On the mechanism of reduction of M(H2O)mn+ by borohydride: the case of Ag(H2O)2.

The redox potentials of M(H2O)mn+/M0(atom) couples are often far too negative to enable the formation of M0(atom) by most reducing agents. Therefore, one has to reconsider the mechanism of formation of M0-NPs by the bottom-up procedure. A deep and detailed theoretical analysis of the reduction of Ag(H2O)2+ by BH4- points out that silver cations act mainly as catalysts of the reactions BH4- + 4H2O → B(OH)4- + 4H2. However, the transition states of the catalyzed process differ from those of the un-catalyzed process. The formation of (H2O)Ag-H, which is the starting stage for the formation of intermediates with Ag-Ag bonds, is only a side reaction in the process. Experimental evidence of the complexity of the process is presented, by stopped-flow; at least four processes are observed prior to the formation of Ag0-NPs. The spectra of these intermediates differ from those of Ag0atom and Ag2+aq. Though DFT calculations were performed only for silver cations, it is believed that analogous mechanisms are involved in the reductions of other cations.