Electrochemical ammonia synthesis by reduction of nitrate on Au doped Cu nanowires.

Electrochemical nitrate reduction reaction (NO3 -RR) to synthesize valuable ammonia (NH3) is considered as a green and appealing alternative to enable an artificial nitrogen cycle. However, as there are other NO3 -RR pathways present, selectively guiding the reaction pathway towards NH3 is currently challenged by the lack of efficient catalyst. Here, we demonstrate a novel electrocatalyst for NO3 -RR consisting of Au doped Cu nanowires on a copper foam (CF) electrode (Au-Cu NWs/CF), which delivers a remarkable NH3 yield rate of 5336.0 ± 159.2 µg h-1 cm-2 and an exceptional faradaic efficiency (FE) of 84.1 ± 1.0% at -1.05 V (vs. RHE). The 15N isotopic labelling experiments confirm that the yielded NH3 is indeed from the Au-Cu NWs/CF catalyzed NO3 -RR process. The XPS analysis and in situ infrared spectroscopy (IR) spectroscopy characterization results indicated that the electron transfer between the Cu and Au interface and oxygen vacancy synergistically decreased the reduction reaction barrier and inhibited the generation of hydrogen in the competitive reaction, resulting in a high conversion, selectivity and FE for NO3 -RR. This work not only develops a powerful strategy for the rational design of robust and efficient catalysts by defect engineering, but also provides new insights for selective nitrate electroreduction to NH3.

Metal Nanocatalyst Sintering Interrogated at Complementary Length Scales.

Metal nanoparticle (NP) sintering is a prime cause of catalyst degradation, limiting its economic lifetime and viability. To date, sintering phenomena are interrogated either at the bulk scale to probe averaged NP properties or at the level of individual NPs to visualize atomic motion. Yet, "mesoscale" strategies which bridge these worlds can chart NP populations at intermediate length scales but remain elusive due to characterization challenges. Here, a multi-pronged approach is developed to provide complementary information on Pt NP sintering covering multiple length scales. High-resolution scanning electron microscopy (HRSEM) and Monte Carlo simulation show that the size evolution of individual NPs depends on the number of coalescence events they undergo during their lifetime. In its turn, the probability of coalescence is strongly dependent on the NP's mesoscale environment, where local population heterogeneities generate NP-rich "hotspots" and NP-free zones during sintering. Surprisingly, advanced in situ synchrotron X-ray diffraction shows that not all NPs within the small NP sub-population are equally prone to sintering, depending on their crystallographic orientation on the support surface. The demonstrated approach shows that mesoscale heterogeneities in the NP population drive sintering and mitigation strategies demand their maximal elimination via advanced catalyst synthesis strategies.

Towards BioMnOx-mediated intra/extracellular electron shuttling for doxycycline hydrochloride metabolism in Bacillus thuringiensis.

Doxycycline hydrochloride (DCH) could be continuously removed by Bacillus thuringiensis S622 with the in-situ biogenic manganese oxide (BioMnOx) via oxidizing/regenerating. The DCH removal rate was significantly increased by 3.01-fold/1.47-fold at high/low Mn loaded via the integration of biological (intracellular/extracellular electron transfer (IET/EET)) and abiotic process (BioMnOx, Mn(III) and •OH). BioMnOx accelerated IET via activating coenzyme Q to enhance electrons transfer (ET) from complex I to complex III, and as an alternative electron acceptor for respiration and provide another electron transfer transmission channel. Additionally, EET was also accelerated by stimulating to secrete flavins, cytochrome c (c-Cyt) and flavin bounded with c-Cyt (Flavins & Cyts). To our best knowledge, this is the first report about the role of BioMnOx on IET/EET during antibiotic biodegradation. These results suggested that Bacillus thuringiensis S622 incorporated with BioMnOx could adopt an alternative strategy to enhance DCH degradation, which may be of biogeochemical and technological significance.

Sulfidation forwarding high-strength Anammox process using nitrate as electron acceptor via thiosulfate-driven nitrate denitratation.

A single up-flow thiosulfate-driven nitrate denitratation coupled with the sulfurized Anammox (TDSA) with the core-shell structure (S0@ Anammox granules) provided a chemical/energy-saving way for the removal of high-content ammonium with nitrate as electron acceptor. Approximately 83.66% total nitrogen removal efficiency (TNRE) could be achieved by the sulfurized Anammox encrusted by S0/Sn2- at a high loading rate (2.6 kg-N/(m3·d)) via resisting high concentration of free ammonia (FA) (22.35 mg/L), mainly through S2O32-, S0/Sn2- -driven partial denitrification-Anammox (PDN-Anammox) process. Moreover, S0/Sn2--PDN-Anammox was largely restricted when intermittently aerated, but still resulting in 74.47% TNRE due to the partial nitrification-Anammox (PN-Anammox). The sequencing analysis revealed that Anammox bacterium (Candidatus_Kuenenia) and sulfur-oxidizing bacterium (Thiobacillus) coexisted, in which Anammox process occurred mainly via NO instead of NH2OH. This study provided a new perspective for high concentration nitrogen wastewater removal in engineering applications.

Atomic layer deposition of ternary ruthenates by combining metalorganic precursors with RuO4 as the co-reactant.

In this work, the use of ruthenium tetroxide (RuO4) as a co-reactant for atomic layer deposition (ALD) is reported. The role of RuO4 as a co-reactant is twofold: it acts both as an oxidizing agent and as a Ru source. It is demonstrated that ALD of a ternary Ru-containing metal oxide (i.e. a metal ruthenate) can be achieved by combining a metalorganic precursor with RuO4 in a two-step process. RuO4 is proposed to combust the organic ligands of the adsorbed precursor molecules while also binding RuO2 to the surface. As a proof of concept two metal ruthenate processes are developed: one for aluminum ruthenate, by combining trimethylaluminum (TMA) with RuO4; and one for platinum ruthenate, by combining MeCpPtMe3 with RuO4. Both processes exhibit self-limiting surface reactions and linear growth as a function of the number of ALD cycles. The observed saturated growth rates are relatively high compared to what is usually the case for ALD. At 100 °C sample temperature, growth rates of 0.86 nm per cycle and 0.52 nm per cycle are observed for the aluminum and platinum ruthenate processes, respectively. The TMA/RuO4 process results in a 1 : 1 Al to Ru ratio, while the MeCpPtMe3/RuO4 process yields a highly Ru-rich composition with respect to Pt. Carbon, hydrogen and fluorine impurities are present in the thin films with different relative amounts for the two investigated processes. For both processes, the as-deposited films are amorphous.

In situ study of the thermal stability of supported Pt nanoparticles and their stabilization via atomic layer deposition overcoating.

Downscaling of supported Pt structures to the nanoscale is motivated by the augmentation of the catalytic activity and selectivity, which depend on the particle size, shape and coverage. Harsh thermal and chemical conditions generally required for catalytic applications entail an undesirable particle coarsening, and consequently limit the catalyst lifetime. Herein we report an in situ synchrotron study on the stability of supported Pt nanoparticles and their stabilization using atomic layer deposition (ALD) as the stabilizing methodology against particle coarsening. Pt nanoparticles were thermally annealed up to 850 °C in an oxidizing environment while recording in situ synchrotron grazing incidence small angle X-ray scattering (GISAXS) 2D patterns, thereby obtaining continuous information about the particle radius evolution. Al2O3 overcoat as a protective capping layer against coarsening via ALD was investigated. In situ data proved that only 1 cycle of Al2O3 ALD caused an augmentation of the onset temperature for particle coarsening. Moreover, the results showed a dependence of the required overcoat thickness on the initial particle size and distribution, being more efficient (i.e. requiring lower thicknesses) when isolated particles are present on the sample surface. The Pt surface accessibility, which is decisive in catalytic applications, was analyzed using the low energy ion scattering (LEIS) technique, revealing a larger Pt surface accessibility for a sample with Al2O3 overcoat than for a sample without a protective layer after a long-term isothermal annealing.

The co-reactant role during plasma enhanced atomic layer deposition of palladium.

Atomic layer deposition (ALD) of noble metals is an attractive technology potentially applied in nanoelectronics and catalysis. Unlike the combustion-like mechanism shown by other noble metal ALD processes, the main palladium (Pd) ALD process using palladium(ii)hexafluoroacetylacetonate [Pd(hfac)2] as precursor is based on true reducing surface chemistry. In this work, a thorough investigation of plasma-enhanced Pd ALD is carried out by employing this precursor with different plasmas (H2*, NH3*, O2*) and plasma sequences (H2* + O2*, O2* + H2*) as co-reactants at varying temperatures, providing insights in the co-reactant and temperature dependence of the Pd growth per cycle (GPC). At all temperatures, films grown with only reducing co-reactants contain a large amount of carbon, while an additional O2* in the co-reactant sequence helps to obtain Pd films with much lower impurity concentrations. Remarkably, in situ XRD and SEM show an abrupt release of the carbon impurities during annealing at moderate temperatures in different atmospheres. In vacuo XPS measurements reveal the remaining species on the as-deposited surface after every exposure. Links are established between the particular surface termination prior to the precursor pulse and the observed differences in GPC, highlighting hydrogen as the key growth facilitator and carbon and oxygen as growth inhibitors. The increase in GPC with temperature for ALD sequences with H2* or NH3* prior to the precursor pulse is explained by an increase in the amount of hydrogen species that reside on the Pd surface which are available for reaction with the Pd(hfac)2 precursor.

Plasma-Enhanced Atomic Layer Deposition of Nanostructured Gold Near Room Temperature.

A plasma-enhanced atomic layer deposition (PE-ALD) process to deposit metallic gold is reported, using the previously reported Me3Au(PMe3) precursor with H2 plasma as the reactant. The process has a deposition window from 50 to 120 °C with a growth rate of 0.030 ± 0.002 nm per cycle on gold seed layers, and it shows saturating behavior for both the precursor and reactant exposure. X-ray photoelectron spectroscopy measurements show that the gold films deposited at 120 °C are of higher purity than the previously reported ones (<1 at. % carbon and oxygen impurities and <0.1 at. % phosphorous). A low resistivity value was obtained (5.9 ± 0.3 µΩ cm), and X-ray diffraction measurements confirm that films deposited at 50 and 120 °C are polycrystalline. The process forms gold nanoparticles on oxide surfaces, which coalesce into wormlike nanostructures during deposition. Nanostructures grown at 120 °C are evaluated as substrates for free-space surface-enhanced Raman spectroscopy (SERS) and exhibit an excellent enhancement factor that is without optimization, only one order of magnitude weaker than state-of-the-art gold nanodome substrates. The reported gold PE-ALD process therefore offers a deposition method to create SERS substrates that are template-free and does not require lithography. Using this process, it is possible to deposit nanostructured gold layers at low temperatures on complex three-dimensional (3D) substrates, opening up opportunities for the application of gold ALD in flexible electronics, heterogeneous catalysis, or the preparation of 3D SERS substrates.

Comparative genomic study of ALDH gene superfamily in Gossypium: A focus on Gossypium hirsutum under salt stress.

Aldehyde dehydrogenases (ALDHs) are a superfamily of enzymes which play important role in the scavenging of active aldehydes molecules. In present work, a comprehensive whole-genomic study of ALDH gene superfamily was carried out for an allotetraploid cultivated cotton species, G. hirsutum, as well as in parallel relative to their diploid progenitors, G. arboreum and G. raimondii. Totally, 30 and 58 ALDH gene sequences belong to 10 families were identified from diploid and allotetraploid cotton species, respectively. The gene structures among the members from same families were highly conserved. Whole-genome duplication and segmental duplication might be the major driver for the expansion of ALDH gene superfamily in G. hirsutum. In addition, the expression patterns of GhALDH genes were diverse across tissues. Most GhALDH genes were induced or repressed by salt stress in upland cotton. Our observation shed lights on the molecular evolutionary properties of ALDH genes in diploid cottons and their alloallotetraploid derivatives. It may be useful to mine key genes for improvement of cotton response to salt stress.

Genome-wide identification of membrane-bound fatty acid desaturase genes in Gossypium hirsutum and their expressions during abiotic stress.

Membrane-bound fatty acid desaturases (FADs) are of great importance and play multiple roles in plant growth and development. In the present study, 39 full-length FAD genes, based on database searches, were identified in tetraploid upland cotton (Gossypium hirsutum L.) and were phylogenetically clustered into four subfamilies. Genomic localization revealed that 34 genes were mapped on 22 chromosomes, and five genes were positioned on the scaffold sequences. The FAD genes of G. hirsutum in the same subfamily had similar gene structures. The structures of paralogous genes were considerably conserved in exons number and introns length. It was suggested that the FAD gene families in G. hirsutum might be duplicated mainly by segmental duplication. Moreover, the FAD genes were differentially expressed in different G. hirsutum tissues in response to different levels of salt and cold stresses, as determined by qRT-PCR analysis. The identification and functional analysis of FAD genes in G. hirsutum may provide more candidate genes for genetic modification.