Efficient Silver(I)-Containing i-Motif DNA Hybrid Catalyst for Enantioselective Diels-Alder Reactions.

The inherent chiral structures of DNA serve as attractive scaffolds to construct DNA hybrid catalysts for valuable enantioselective transformations. Duplex and G-quadruplex DNA-based enantioselective catalysis has made great progress, yet novel design strategies of DNA hybrid catalysts are highly demanding and atomistic analysis of active centers is still challenging. DNA i-motif structures could be finely tuned by different cytosine-cytosine base pairs, providing a new platform to design DNA catalysts. Herein, we found that a human telomeric i-motif DNA containing cytosine-silver(I)-cytosine (C-Ag+-C) base pairs interacting with Cu(II) ions (i-motif DNA(Ag+)/Cu2+) could catalyze Diels-Alder reactions with full conversions and up to 95% enantiomeric excess. As characterized by various physicochemical techniques, the presence of Ag+ is proved to replace the protons in hemiprotonated cytosine-cytosine (C:C+) base pairs and stabilize the DNA i-motif to allow the acceptance of Cu(II) ions. The i-motif DNA(Ag+)/Cu2+ catalyst shows about 8-fold rate acceleration compared with DNA and Cu2+. Based on DNA mutation experiments, thermodynamic studies and density function theory calculations, the catalytic center of Cu(II) ion is proposed to be located in a specific loop region via binding to one nitrogen-7 atom of an unpaired adenine and two phosphate-oxygen atoms from nearby deoxythymidine monophosphate and deoxyadenosine monophosphate, respectively.

Confinement effects on the structure and reactivity of encapsulated buckybowls in cycloparaphenylene.

We theoretically investigated the host-guest chemistry between belt-like cycloparaphenylenes (CPPs) and entrapped bowl-shaped sumanene and corannulene. Density functional theory calculations show that the buckybowls can be stabilized in a CPP host with an appropriately sized cavity (e.g., [10]CPP) through multi-site CH-π interactions. Arising from the confined intermolecular interactions within the cavity, the restrictive buckybowls display novel reactivity distinct from that in their free state.

The meso-substituent electronic effect of Fe porphyrins on the electrocatalytic CO2 reduction reaction.

We report Fe porphyrins bearing different meso-substituents for the electrocatalytic CO2 reduction reaction (CO2RR). By replacing two and four meso-phenyl groups of Fe tetraphenylporphyrin (FeTPP) with strong electron-withdrawing pentafluorophenyl groups, we synthesized FeF10TPP and FeF20TPP, respectively. We showed that FeTPP and FeF10TPP are active and selective for CO2-to-CO conversion in dimethylformamide with the former being more active, but FeF20TPP catalyzes hydrogen evolution rather than the CO2RR under the same conditions. Experimental and theoretical studies revealed that with more electron-withdrawing meso-substituents, the Fe center becomes electron-deficient and it becomes difficult for it to bind a CO2 molecule in its formal Fe0 state. This work is significant to illustrate the electronic effects of catalysts on binding and activating CO2 molecules and provide fundamental knowledge for the design of new CO2RR catalysts.

Multi-process production occurs in the iron and steel industry, supporting 'dual carbon' target: An in-depth study of CO2 emissions from different processes.

Reducing CO2 emissions of the iron and steel industry, a typical heavy CO2-emitting sector, is the only way that must be passed to achieve the 'dual-carbon' goal, especially in China. In previous studies, however, it is still unknown what is the difference between blast furnace-basic oxygen furnace (BF-BOF), scrap-electric furnace (scrap-EF) and hydrogen metallurgy process. The quantitative research on the key factors affecting CO2 emissions is insufficient. There is also a lack of research on the prediction of CO2 emissions by adjusting industrial structure. Based on material flow analysis, this study establishes carbon flow diagrams of three processes, and then analyze the key factors affecting CO2 emissions. CO2 emissions of the iron and steel industry in the future is predicted by adjusting industrial structure. The results show that: (1) The CO2 emissions of BF-BOF, scrap-EF and hydrogen metallurgy process in a site are 1417.26, 542.93 and 1166.52 kg, respectively. (2) By increasing pellet ratio in blast furnace, scrap ratio in electric furnace, etc., can effectively reduce CO2 emissions. (3) Reducing the crude steel output is the most effective CO2 reduction measure. There is still 5.15 × 108-6.17 × 108 tons of CO2 that needs to be reduced by additional measures.

Muti-objective optimization on energy consumption, CO2 emission and production cost for iron and steel industry.

Due to high material density, high energy consumption density and CO2 emission density, it is not only difficult but significant to clarify the relationship between energy consumption, the CO2 emission and the production cost in different conditions. However, the previous researches rarely refer how to balance the energy consumption, the CO2 emission and the production cost after the fluctuation of material, energy and carbon price as well as what will happen to them if production structure changes. Therefore, based on the conservation law of mass and energy, to study iron and steel manufacturing process (ISMP), this paper, taking carbon price into consideration, establishes a muti-optimization model of energy consumption, CO2 emission and cost. After optimization with different objectives, the production cost per tonne of crude steel is reduced by 192.03 CNY (7.71%), the CO2 emission per tonne of crude steel is reduced by 224.22 kg (13.37%), and the energy consumption per tonne of steel is reduced by 51.20 kgce (9.10%). Moreover, based on the optimization results under different objectives, it is ironmaking process (coal ratio and ore ratio) and steelmaking process (amount of scrap steel) that has more impact on three above as well as ore blending and coal blending have a great influence on production cost but little effect on energy consumption and CO2 emission.

Defective hBN-Supported Fe2N Single Cluster Catalyst for Active and Selective Electro-Reduction of Multiple CO to Propane: Theoretical Elucidation of Metal-Nonmetal Synergic Effects.

The present work introduces the multiple CO reduction toward C3 products promoted by a newly designed single cluster catalyst consisting of defective hBN and embedded dimerized Fe, by means of density functional theory calculations. We find the strong metal-support interactions give rise to the local strain and electron accumulation of the N coordinated with two metals and resultantly form a Fe2N active center. The metal-nonmetal synergic effect facilitates the coadsorption and C-C coupling of triple CO molecules and finally generates propane in a highly active and selective way.

Difference in calcium ion precipitation between free and immobilized Halovibrio mesolongii HMY2.

Biomineralization has become a research focus in wastewater treatment due to its much lower costs compared to traditional methods. However, the low sodium chloride (NaCl)-tolerance of bacteria limits applications to only water with low NaCl concentrations. Here, calcium ions in hypersaline wastewater (10% NaCl) were precipitated by free and immobilized Halovibrio mesolongii HMY2 bacteria and the differences between them were determined. The results show that calcium ions can be transformed into several types of calcium carbonate with a range of morphologies, abundant organic functional groups (C-H, C-O-C, C=O, etc), protein secondary structures (ß-sheet, α-helix, 310 helix, and ß-turn), P=O and S-H indicated by P2p and S2p, and more negative δ13CPDB (‰) values (-16.8‰ to -18.4‰). The optimal conditions for the immobilized bacteria were determined by doing experiments with six factors and five levels and using response surface method. Under the action of two groups of immobilized bacteria prepared under the optimal conditions, by the 10th day, Ca2+ ion precipitation ratios had increased to 79%-89% and 80%-88% with changes in magnesium ion cencentrations. Magnesium ions can significantly inhibit the calcium ion precipitation, and this inhibitory effect can be decreased under the action of immobilized bacteria. Minerals induced by immobilized bacteria always aggregated together, had higher contents of Mg, P, and S, lower stable carbon isotope values and less well-developed protein secondary structures. This study demonstrates an economic and eco-friendly method for recycling calcium ions in hypersaline wastewater, providing an easy step in the process of desalination.

Synthesis of Template-Free ZSM-5 from Rice Husk Ash at Low Temperatures and Its CO2 Adsorption Performance.

In this paper, a green synthesis method for ZSM-5 zeolite is explored to reduce the synthesis cost, environmental hazard, and reaction temperatures. For the ZSM-5 samples prepared at low temperatures, the influence of factors such as the hydrothermal temperature, crystallization time, and the number of seeds is systematically investigated. The adsorption isotherm of CO2 is used for fitting analysis of adsorption models and determination of the adsorption selectivity. The results show that the best one among the three samples presents the highest CO2 adsorption capacity of 2.39 mmol/g at 273 K and 15 bar. It is prepared with a hydrothermal temperature of 393 K, crystallization time of 7 days, and a seed crystal of 1 wt %. The dual-site Langmuir model can well describe the experimental data, indicating that double adsorption sites rather than the simple single-layer adsorption are dominant in samples. As the pressure increases, the adsorption capacity calculated by the model is much lower than the actual value with a deviation index of 12.5%. At a pressure of 1 bar, the optimal selectivity is attained with sample L-20, viz., CO2/N2 of 34.3 and CO2/O2 of 70.2. The green synthesis method reported in this research can be used to successfully prepare ZSM-5 zeolite, and it shows excellent CO2 adsorption performance. In addition, the use of low-cost raw materials and template-free synthesis methods will facilitate the large-scale application of green synthesis processes in the future.

CO2 and water vapor adsorption properties of framework hybrid W-ZSM-5/silicalite-1 prepared from RHA.

Framework hybrid W-ZSM-5 and W-silicalite-1 zeolites were synthesized by hydrothermal methods using rice husk ash (RHA) as a silicon raw material. RHA is a low-cost precursor material, and its use can also alleviate the environmental and human health related problems that may occur when it is stacked in open fields. A series of comparative samples were characterized by XRD, FTIR, ICP-OES, SEM, N2 adsorption-desorption and pore size analysis in order to examine their crystal structure, hybrid state, morphology and textural properties. The maximum CO2 adsorption capacities of W-ZSM-5 and W-silicalite-1 are 81.69 and 69.96 cm3 g-1, respectively, measured at 15 bar. The isotherms of CO2, N2 and O2 are perfectly fitted by the Toth model, and it is noted that the presence of Al atoms increases the heterogeneity. It can be seen that the greater the heterogeneity of the adsorbent, the larger the CO2 adsorption capacity achieved. The incorporation of tungsten into the framework does not affect the crystallization of the zeolite, but it prevents the formation of silanol and O-H groups at the adsorption sites. Therefore, the CO2/H2O selectivity of W-ZSM-5 is slightly higher than that of ZSM-5, and that of W-silicalite-1 is three times that of silicalite-1. W-ZSM-5/silicalite-1 are promising adsorbents for separating CO2 under humid industrial conditions.

An evaluation of greenhouse gas emission efficiency in China's industry based on SFA.

As one of the largest countries with sound industrial systems in the world, China is a major emitter of greenhouse gases. In order to achieve sustainable development, the analysis of greenhouse gas emissions from industry is of great significance. This research evaluates the greenhouse gas emission efficiency (GHG efficiency) at industry level in 26 sectors of China and analyzes the impacts of its determinants using stochastic frontier approach. Furthermore, the correlations for GHG efficiency with its determinants and other proxies are estimated by Kendall's rank analysis. Industry level data from Chinese processing and manufacturing industries spanning over the period 2000-2016 are used for this analysis. Results show that there has little potential to improve GHG efficiency, then technology progress is necessary. The GHG efficiency performance responds both to changes in the proportion of net electricity use and the ratio of electricity price to coal price; meanwhile the technology capacity also has a positive impact. Besides, three main proxies of GHG intensity, energy efficiency and energy intensity have their own significance respectively, but could not represent GHG efficiency.