Three parallel algorithms for classical molecular dynamics are presented. The first assigns each processor a fixed subset of atoms; the second assigns each a fixed subset of inter-atomic forces to compute; the third assigns each a fixed spatial region. The algorithms are suitable for molecular dynamics models which can be difficult to parallelize efficiently—those with short-range forces where the neighbors of each atom change rapidly. They can be implemented on any distributed-memory parallel machine which allows for message-passing of data between independently executing processors. The algorithms are tested on a standard Lennard-Jones benchmark problem for system sizes ranging from 500 to 100,000,000 atoms on several parallel supercomputers--the nCUBE 2, Intel iPSC/860 and Paragon, and Cray T3D. Comparing the results to the fastest reported vectorized Cray Y-MP and C90 algorithm shows that the current generation of parallel machines is competitive with conventional vector supercomputers even for small problems. For large problems, the spatial algorithm achieves parallel efficiencies of 90% and a 1840-node Intel Paragon performs up to 165 faster than a single Cray C9O processor. Trade-offs between the three algorithms and guidelines for adapting them to more complex molecular dynamics simulations are also discussed.

Fast parallel algorithms for short-range molecular dynamics

: The unpolarized absorption and circular dichroism spectra of the fundamental vibrational transitions of the chiral molecule, 4-methyl-2-oxetanone, are calculated ab initio. Harmonic force fields are obtained using Density Functional Theory (DFT), MP2, and SCF methodologies and a 5S4P2D/3S2P (TZ2P) basis set. DFT calculations use the Local Spin Density Approximation (LSDA), BLYP, and Becke3LYP (B3LYP) density functionals. Mid-IR spectra predicted using LSDA, BLYP, and B3LYP force fields are of significantly different quality, the B3LYP force field yielding spectra in clearly superior, and overall excellent, agreement with experiment. The MP2 force field yields spectra in slightly worse agreement with experiment than the B3LYP force field. The SCF force field yields spectra in poor agreement with experiment.The basis set dependence of B3LYP force fields is also explored: the 6-31G* and TZ2P basis sets give very similar results while the 3-21G basis set yields spectra in substantially worse agreements with experiment. jg

Ab initio calculation of vibrational absorption and circular dichroism spectra using density functional force fields

It is well known that urbanization and industrialization have resulted in the rapidly increasing emissions of volatile organic compounds (VOCs), which are a major contributor to the formation of secondary pollutants (e.g., tropospheric ozone, PAN (peroxyacetyl nitrate), and secondary organic aerosols) and photochemical smog. The emission of these pollutants has led to a large decline in air quality in numerous regions around the world, which has ultimately led to concerns regarding their impact on human health and general well-being. Catalytic oxidation is regarded as one of the most promising strategies for VOC removal from industrial waste streams. This Review systematically documents the progresses and developments made in the understanding and design of heterogeneous catalysts for VOC oxidation over the past two decades. It addresses in detail how catalytic performance is often drastically affected by the pollutant sources and reaction conditions. It also highlights the primary routes for catalyst deactivation and discusses protocols for their subsequent reactivation. Kinetic models and proposed oxidation mechanisms for representative VOCs are also provided. Typical catalytic reactors and oxidizers for industrial VOC destruction are further discussed. We believe that this Review will provide a great foundation and reference point for future design and development in this field.

/pdf/recent-advances-in-the-catalytic-oxidation-of-volatile-zw2c35dbg7.pdf

Recent Advances in the Catalytic Oxidation of Volatile Organic Compounds: A Review Based on Pollutant Sorts and Sources.

Selective catalytic reduction with NH3 (NH3-SCR) is the most efficient technology to reduce the emission of nitrogen oxides (NOx) from coal-fired industries, diesel engines, etc. Although V2O5-WO3(MoO3)/TiO2 and CHA structured zeolite catalysts have been utilized in commercial applications, the increasing requirements for broad working temperature window, strong SO2/alkali/heavy metal-resistance, and high hydrothermal stability have stimulated the development of new-type NH3-SCR catalysts. This review summarizes the latest SCR reaction mechanisms and emerging poison-resistant mechanisms in the beginning and subsequently gives a comprehensive overview of newly developed SCR catalysts, including metal oxide catalysts ranging from VOx, MnOx, CeO2, and Fe2O3 to CuO based catalysts; acidic compound catalysts containing vanadate, phosphate and sulfate catalysts; ion exchanged zeolite catalysts such as Fe, Cu, Mn, etc. exchanged zeolite catalysts; monolith catalysts including extruded, washcoated, and metal-mesh/foam-based monolith catalysts. The challenges and opportunities for each type of catalysts are proposed while the effective strategies are summarized for enhancing the acidity/redox circle and poison-resistance through modification, creating novel nanostructures, exposing specific crystalline planes, constructing protective/sacrificial sites, etc. Some suggestions are given about future research directions that efforts should be made in. Hopefully, this review can bridge the gap between newly developed catalysts and practical requirements to realize their commercial applications in the near future.

Selective Catalytic Reduction of NOx with NH3 by Using Novel Catalysts: State of the Art and Future Prospects.

Heavy metals like arsenic, copper, cadmium, chromium, nickel, zinc, lead, and mercury are major pollutants of fresh water reservoirs because of their toxic, non-biodegradable, and persistent nature. The industrial growth is the major source of heavy metals introducing such pollutants into different segments of the environment including air, water, soil, and biosphere. Heavy metals are easily absorbed by fishes and vegetables due to their high solubility in the aquatic environments. Hence, they may accumulate in the human body by means of the food chain. Various methods have been developed and used for water and wastewater treatment to decrease heavy metal concentrations. These technologies include membrane filtration, ion-exchange, adsorption, chemical precipitation, nanotechnology treatments, electrochemical and advanced oxidation processes. In this review, the methods as well as their mechanisms and efficiency are discussed.

Removal of Heavy Metals from Industrial Wastewaters: A Review

Transition metal (cerium and cobalt) doped γ-MnO2 (M-γ-MnO2, where M represents Ce, Co) catalysts were successfully synthesized and characterized. Cerium-doped γ-MnO2 materials showed ozone (O3) conversion of 96% for 40 ppm of O3 under relative humidity (RH) of 65% and space velocity of 840 L g–1 h–1 after 6 h at room temperature, which is far superior to the performance of the Co-γ-MnO2 (55%) and γ-MnO2 (38%) catalysts. Under space velocity of 840 L g–1 h–1, the conversion of ozone over the Ce-γ-MnO2 catalyst under RH = 65% and dry conditions within 96 h was 60% and 100%, respectively, indicating that it is a promising material for ozone decomposition. XRD and HRTEM data suggested that Ce-γ-MnO2 formed mixed crystals consisting of α-MnO2 and γ-MnO2 with specific surface area increased from 74 m2/g to 120 m2/g compared to undoped γ-MnO2, thus more surface defects were introduced. H2-TPR, O2-TPD, XPS, Raman, and EXAFS confirmed that Ce-γ-MnO2 exhibited more surface oxygen vacancies and surface defects, whi...

Oxygen Vacancies Induced by Transition Metal Doping in γ-MnO2 for Highly Efficient Ozone Decomposition.

The structure of dispersed vanadyl species plays a crucial role in the selective catalytic reduction (SCR) of NO with NH 3 over vanadia-based catalysts. Here, we demonstrate that the polymeric vanadyl species have a markedly higher NH 3 -SCR activity than the monomeric vanadyl species. The coupling effect of the polymeric structure not only shortens the reaction pathway for the regeneration of redox sites but also substantially reduces the overall reaction barrier of the catalytic cycle. Therefore, it is the polymeric vanadyl species, rather than the monomeric vanadyl species, that determine the NH 3 -SCR activity of vanadia-based catalysts, especially under low-temperature conditions. The polymeric vanadia-based SCR mechanism reported here advances the understanding of the working principle of vanadia-based catalysts and paves the way toward the development of low vanadium–loading SCR catalysts with excellent low-temperature activity.

https://advances.sciencemag.org/content/advances/4/11/eaau4637.full.pdf

Polymeric vanadyl species determine the low-temperature activity of V-based catalysts for the SCR of NOx with NH3

The electrocatalytic reduction of CO2 (CO2ER) to liquid fuels is important for solving fossil fuel depletion. However, insufficient insight into the reaction mechanisms renders a lack of effective regulation of liquid product selectivity. Here, in situ surface-enhanced Raman spectroscopy (SERS) empowered by 13C/12C isotope exchange is applied to probing the CO2ER process on nanoporous silver (np-Ag). Direct spectroscopic evidence of the preliminary intermediates, *COOH and *OCO-, indicates that CO2 is coordinated to the catalyst via diverse adsorption modes. Further, the relative Raman intensities of the above intermediates vary notably on np-Ag modified by Cu or Pd, and the liquid product selectivity also changes accordingly. Combined with density functional theory calculations, this study demonstrates that the CO2 adsorption configuration is a critical factor governing the reaction selectivity. Meanwhile, *COOH and *OCO- are key targets in the initial stage regulating liquid product selectivity, which could facilitate future selective catalyst design.

In-Situ Surface-Enhanced Raman Spectroscopic Evidence on the Origin of Selectivity in CO2 Electrocatalytic Reduction

The Fenton reaction has been explored extensively in different fields due to the generation of hydroxyl radicals (˙OH). However, the reaction requires strongly acidic conditions and excessive consumption of H2O2, which impede its widespread application. Here, we report that twice the amount of ˙OH radicals as that of the reacted H2O2 was formed by the reaction of H2O2 with a type of nano-composite OH–CCN/CuCo–Al2O3 under nearly neutral conditions. The nano-composite was achieved by the co-incorporation of Cu and Co into γ-Al2O3, and the sequential complex formation of the σ-type Cu–O–C linker between the surface Cu and the hydroxyl group of the tri-s-triazine ring in C-g-C3N4. From electron paramagnetic resonance spectra and density functional theory simulations, it was verified that an electron-rich area around Cu occurred due to the Cu–π interaction and the different electronegativities of Cu with Co and Al in OH–CCN/CuCo–Al2O3, which reacted with H2O2, resulting in two electron transfer processes. One process is from the electron-rich Cu center to H2O2 to form ˙OH, and the other is from H2O to the N atom of OH–CCN to produce ˙OH. The catalyst shows extremely high activity for the degradation of various refractory organic pollutants in water under mild conditions with a high utilization efficiency of H2O2 (∼90%). Our findings confirm that the construction of an electron-rich area is essential for overcoming the limitations of the classical Fenton process for environmental remediation and other applications.

Selective H2O2 conversion to hydroxyl radicals in the electron-rich area of hydroxylated C-g-C3N4/CuCo–Al2O3

Ammonia (NH3) has potentially harmful effects on human health and has recently been found to be an important factor in the formation of haze; thus, its emission control is urgent, especially during haze pollution periods. In this work, two kinds of Ag/Al2O3 catalysts with different Al2O3 particle sizes (micro-Al2O3 and nano-Al2O3) were prepared and tested for the selective catalytic oxidation of ammonia (NH3-SCO). It was shown that Ag/nano-Al2O3 was much more active than Ag/micro-Al2O3 for NH3-SCO in the low-temperature range. The results of characterization by BET, TEM, NH3-TPD, XRD, H2-TPR, UV–vis, and XAFS revealed that Ag/nano-Al2O3 possesses much smaller Ag particles and more metallic Ag species (AgNPs) and also contains abundant acid sites, which facilitate the adsorption and dissociation of NH3, therefore resulting in much higher NH3-SCO activity. In addition, on the basis of in situ DRIFTS, kinetic measurements, and DFT calculation results, we discovered that the NH3-SCO reaction over Ag/nano-Al2O...

Guangzhi He

Papers

Oxygen Vacancies Induced by Transition Metal Doping in γ-MnO2 for Highly Efficient Ozone Decomposition.

Polymeric vanadyl species determine the low-temperature activity of V-based catalysts for the SCR of NOx with NH3

In-Situ Surface-Enhanced Raman Spectroscopic Evidence on the Origin of Selectivity in CO2 Electrocatalytic Reduction

Selective H2O2 conversion to hydroxyl radicals in the electron-rich area of hydroxylated C-g-C3N4/CuCo–Al2O3

Nanosize Effect of Al2O3 in Ag/Al2O3 Catalyst for the Selective Catalytic Oxidation of Ammonia