The 100th anniversary of a leading nitrogen fixation technology developer like CASALE SA is a reason to reflect over the 20th century successful solution of the problem of world food supply, and to look out for solutions for sustainable developments with respect to ammonia production. We review the role of nitrogen as essential chemical constituent in photosynthesis and biology, and component of ammonia as it is used as fertilizer for primary production by photosynthesis for farming and food supply and its future role as energy carrier. While novel synthesis methods and very advanced synchrotron based x-ray analytical techniques are being developed, we feel it is important to refer to the historical and economical context of nitrogen. The breaking of the N≡N triple bond remains a fundamental chemical and energetic problem in this context. We review the electrochemical ammonia synthesis as an energetically and environmentally benign method. Two relatively novel X-ray spectroscopy methods, which are relevant for the molecular understanding of the catalysts and biocatalysts, i.e. soft X-ray absorption spectroscopy and nuclear resonant vibration spectroscopy are presented. We illustrate the perceived reality in fertilizer usage on the field, and fertilizer production in the factory complex with photos and thus provide a contrast to the academic view of the molecular process of ammonia function and production.

The dehydrogenation and dehydration of formic acid is investigated on the -MoC (100) catalyst surface using time independent density functional theory. The energetics of the two mechanisms are calculated, and the thermochemistry and kinetics are discussed using the transition state theory. Subsequently, microkinetic modelling of the system is conducted, considering the batch reactor model. The potential energy landscape of the reaction shows a thermodynamically favourable cleavage of H-COOH to form CO; however, the kinetics show that the dehydrogenation mechanism is faster and CO is continuously formed. The effect of HCOOH adsorption on the surface is also analysed, in a temperature-programmed desorption, with the conversion proceeding at under 350 K and desorption of CO is observed with a selectivity of about 100 %, in line with the experimental reports.

A unified treatment of the renewable portfolio standards is given concerning direct methanol fuel. The current mechanism of electrocatalysis of methanol oxidation on platinum and non-platinum-containing alloys is summarized for the systematic improvement of the rate of electro-oxidation of methanol are discussed. Policy realignment under the five-year plan is discussed in length to demonstrate how policy, markets, and engineering designs contribute towards the development of model direct methanol fuel cells operational enhancement, and factors that affect critical performance parameters for commercial exploitation are summarized for catalytic formulations and cell design within the context of why this investment in technology, education, and finances is required within the global context of sustainable energy and energy independence as exposed by thirteenth the five-year plan. The prolog focuses on the way, whereas the section on methanol fuel cells on the how and the post log on what is expected post-COVID-19 era in science and technology as China pivots to a post-fossil fuel economy. China's industrial growth has been through internal market reforms and supplies side economics from the Chinese markets for fossil fuels except for petroleum. The latest renewable portfolio standards adopted have common elements as adopted from North American and the United Kingdom in terms of adaptation of obligation in terms of renewable portfolio standards as well as a realization that the necessity for renewables standards for the thirteen five year plan (from 2016 to 2020) need to less rigorously implemented due to performance targets that were met during the eleventh (06-10) and twelfth five-year plans (11-15) in terms of utilization of small coal-ire power plants, development of newer standards, led to an improvement of energy efficiency of 15 %, reduction of SO/NO by an average of 90 % and PM2.5 by 96 % over the last two five-year plans. The current phase of the plan has a focus on energy generation from coal and a slowing down of renewables or Renewable energy curtailment of approximately 400 T Wh renewables including 300 T Wh of non-hydro power, principally from Guangdong, and Jiangsu for transfer of hydropower and Zhejiang, Tianjin, Henan for non-hydro power transfer with Beijing and Shanghai playing important roles in renewables energy curtailment and realignment using an integrated approach to optimize each provinces energy portfolio. The realignment of the renewable energy portfolio indicates that the newly installed capacity in Sichuan, Yunnan, Inner Mongolia, and Zhejiang will account for less than 20 % of the current renewable energy portfolio but with the NO SO and PM savings already accrued. The catalytic reduction of carbon dioxide to methanol (70 / 110 million metric tons from all sources in 2019 for China/world) is one technological approach to reduce global carbon dioxide emissions and suggests that catalytic methanol synthesis by CO hydrogenation may be a plausible approach, even if it is more expensive economically than methanol synthesis by the syngas approach. This is because the CO emissions of the synthesis are lower than other synthesis methodologies. The Chinese government has placed a premium on cleaner air and water and may view such an approach as solving the dual issues of fuel substitution and reduction of CO. Thus, the coupling of hydrogen generation from sustainable energies sources (Solar 175 / 509 GW) or wind (211/591.5 GW in 2019) may be an attractive approach, as this requires slightly less water than coal gasification. Due to the thermodynamic requirement of lower operating pressure and higher operating pressure, currently, there is no single operational approach, although some practice approaches (220 °C at 48 atm using copper) and zinc oxide/alumina are suggested for optimal performance.

A novel porous ceramic sheet supported nickel particles reactor was obtained by an preparation method. This reactor was then used to investigate continuous-flow catalysis of nitroaromatic compounds and methyl orange. The details of the structure and morphology were characterized by XRD, SEM, XPS, Raman, element mapping, mercury intrusion method and Archimedes principle. The porous ceramic sheet supported Ni particles reactor exhibited excellent catalytic performance in the catalytic reduction of -nitrophenol and methyl orange by sodium borohydride at room temperature. Both the conversion of -nitrophenol (5 mM) and methyl orange (0.3 mM) reached nearly 100% at the injection speed of 2.67 mL·min. In addition, it maintained conversions of 100% after 10 recycling time since the porous ceramic sheet could reduce the aggregation for Ni particles. Furthermore, the chemisorbed oxygen, and the strong interaction between Ni and porous ceramic sheet resulted in a highly efficient, recoverable, and cost-effective multifunctional reactor. All of these advantages present new opportunities to be implemented in the field of waste water treatment and environmental toxicology. Ultimately, the porous ceramic sheet could also support other metal nanomaterial, and used in other fields of environmental catalysis.

A novel and recoverable platform of polyurethane (PU) sponge-supported Au nanoparticle catalyst was obtained by a water-based in-situ preparation process. The structure, chemical, and morphology properties of this platform were characterized by XRD, TGA, SEM, FT-IR, and XPS. The Au/PU sponge platform exhibited excellent catalytic performances in catalytic reductions of -nitrophenol and -nitroaniline at room temperature, and both catalytic reactions could be completed within 4.5 and 1.5 min, respectively. Furthermore, the strong interaction between Au nanoparticles and the PU sponge enabled the catalyst system to maintain a high catalytic efficiency after 5 recycling times, since the PU sponge reduced the trend of leaching and aggregation of Au nanoparticles. The unique nature of Au nanoparticles and the porous PU sponge along with their strong interaction resulted in a highly efficient, recoverable, and cost-effective multifunctional catalyst. The AuNP/Sponge nanocatalyst platform has great potential for wide environmental and other catalytic applications.

A series of TiO catalyst carriers with ceria additives were prepared by a precipitation method and tested for selective catalytic reduction (SCR) of NO by NH. These samples were characterized by XRD, N-BET, NH-TPD, H-TPR, TEM, XPS and DRIFTS, respectively. Results showed that the appropriate addition of ceria can enhance the catalytic activity and thermostability of TiO catalyst carriers significantly. The maximum catalytic activity of Ti-Ce-O-500 is 98.5% at 400 °C with a GHSV of 100 000 h and the high catalytic activity still remains even after the treatment at high temperature for 24 h. The high catalytic performance of Ti-Ce-O-500 can be attributed to a series of superior properties, such as larger specific surface area, more Brønsted acid sites, more hydrogen consumption, and the higher proportion of chemisorbed oxygen. Ceria atoms can inhibit the crystalline grain growth and the collapse of small channels caused by high temperatures. Furthermore, DRIFTS in different feed gases show that the SCR reaction over Ti-Ce-O-500 follows both E-R and L-H mechanisms.

Octahedral anatase particles (OAPs) were modified with silver nanoparticles (NPs) by photodeposition method. The properties of OAPs influenced the properties of silver deposits, and thus the photocatalytic activity of the obtained silver-modified OAPs. Photocatalytic activities were tested under UV and vis irradiation for oxidative decomposition of acetic acid and oxidation of 2-propanol, respectively. The properties of silver-modified OAPs were investigated by XRD, STEM, DRS, XPS and time-resolved microwave conductivity (TRMC) method. It was found that electron traps (ETs) worked as nucleation sites for silver, resulting in formation of smaller silver NPs on smaller OAPs with larger content of ETs. The modification with silver resulted in enhanced photocatalytic activity under both UV and vis irradiation. It was found that larger crystallite size of silver NPs, and thus larger polydispersity of silver deposits resulted in broad and intense plasmon resonance peak causing enhanced visible activity. The correlation between photocatalytic activity and TRMC data, e.g., slower decay of TRMC signal for more active samples, allowed discussion on property-governed photocatalytic activities of silver-modified titania.

The Haber-Bosch process is a major contributor to fixed nitrogen that supports the world's nutritional needs and is one of the largest-scale industrial processes known. It has also served as a testing ground for chemists' understanding of surface chemistry. Thus, it is significant that the most thoroughly developed catalysts for N reduction use potassium as an electronic promoter. In this review, we discuss the literature on alkali metal cations as promoters for N reduction, in the context of the growing knowledge about cooperative interactions between N, transition metals, and alkali metals in coordination compounds. Because the structures and properties are easier to characterize in these compounds, they give useful information on alkali metal interactions with N. Here, we review a variety of interactions, with emphasis on recent work on iron complexes by the authors. Finally, we draw conclusions about the nature of these interactions and areas for future research.

The reduction of carbon dioxide to chemical fuels such as carbon monoxide is an important challenge in the field of renewable energy conversion. Given the thermodynamic stability of carbon dioxide, it is difficult to efficiently activate this substrate in a selective fashion and the development of new electrocatalysts for CO reduction is of prime importance. To this end, we have prepared and studied a new -Re(CO) complex supported by a bipyridine ligand containing ancillary BODIPY moieties (). Voltammetry experiments revealed that this system displays a rich redox chemistry under N, as can be reduced by up to four electrons at modest potentials. These redox events have been characterized as the Re couple, and three ligand based reductions - two of which are localized on the BODIPY units. The ability of the ligand to serve as a non-innocent redox reservoir is manifest in an enhanced electrocatalysis with CO as compared to an unsubstituted Re-bipyridine complex lacking BODIPY units (). The second order rate constant for reduction of CO by was measured to be = 3400 Ms at an applied potential of -2.0 V versus SCE, which is roughly three times greater than the corresponding unsubstituted Re-bipyridine homologue. Photophysical and photochemical studies were also carried out to determine if was a competent platform for CO reduction using visible light. These experiments showed that this complex supports unusual excited state dynamics that precludes efficient CO reduction and are distinct from those that are typically observed for -Re(CO) complexes.

(anamorph ) is a saprophytic fungus that produces hydrolases, which are applied in different types of industries and used for the production of biofuel. A recombinant strain, which constantly expresses the main transcription activator of hydrolases (Xylanase regulator 1), was found to grow faster on xylan and its monomeric backbone molecule d-xylose. This strain also showed improved ability of clearing xylan medium on plates. Furthermore, this strain has a changed transcription profile concerning genes encoding for hydrolases and enzymes associated with degradation of (hemi)celluloses. We demonstrated that enzymes of this strain from a xylan cultivation favoured break down of hemicelluloses to the monomer d-xylose compared to the parental strain, while the enzymes of the latter one formed more xylobiose. Applying supernatants from cultivation on carboxymethylcellulose in enzymatic conversion of hemicelluloses, the enzymes of the recombinant strain were clearly producing more of both, d-xylose and xylobiose, compared to the parental strain. Altogether, these results point to a changed hydrolase expression profile, an enhanced capability to form the xylan-monomer d-xylose and the assumption that there is a disordered induction pattern if the Xylanase regulator 1 is de-regulated in .

The oxidation of the endocrine disruptor, diethylstilbestrol (DES) in aqueous media by ultrasound is significantly enhanced by Fe(II) catalyst. The observed enhancement is likely the result of increased levels of hydroxyl radicals from the iron-promoted reduction of the hydrogen peroxide produced during ultrasonic irradiation. The degradation is effective over a range of concentrations and is consistent with pseudo first-order kinetics. Relatively high concentrations of hydrogen peroxide, ~450 mM, are present in solution under our experimental conditions after 1 h of ultrasonic irradiation (665 kHz). The concentration of HO in solution decreased with the addition of Fe(II) along with an increase in the degradation of DES. Hydrogen peroxide alone does not appreciably degrade DES. Our results demonstrate ultrasonic-induced degradation of DES can be accelerated with the addition of Fe(II). The combination of ultrasonic irradiation and Fe(II)-promoted conversion of HO to hydroxyl radical may provide a valuable strategy for the treatment of organic pollutants.

Graphitic carbon nitride supported palladium nanoparticles, Pd@g-CN, have been synthesized and utilized for the direct oxidative esterification of alcohols using atmospheric oxygen as a co-oxidant photocatalytic C-H activation.