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721.
水热污泥与煤在混燃过程中的协同效应特性研究 总被引:1,自引:0,他引:1
水热污泥与煤在混燃过程中的协同效应特性研究 《燃料化学学报》2018,46(12):1437-1446
以城市污泥衍生的水热污泥(SS-derived hydrochar)为对象,结合傅里叶红外光谱分析(FT-IR)、X射线荧光光谱分析(XRF)和X射线衍射分析(XRD)等对比研究了水热污泥与三种不同品阶煤(褐煤、烟煤和无烟煤)在有机/无机结构与燃料特性上的异同;同时,通过热重(TG)与偏差分析(Deviation)考察水热污泥与各阶煤在不同混合比例条件下的协同燃烧行为及其作用机制。结果表明,污泥经过水热处理后其有机结构和燃烧行为均提升至与煤相似的水平,该过程不仅改善污泥的燃烧特性,并增强其与煤之间的协同燃烧效应。水热污泥中适量的轻质组分与(碱)碱土金属能在混合燃烧过程中加速煤的失重速率,其对三种煤的促进作用可达4.4%-16.1%(褐煤)、1.9%-9.4%(烟煤)和4.8%-12.1%(无烟煤)。总体而言,水热污泥与褐煤混合而成的燃料在燃料性能上具有较大的优势,并且其混合比例以30%(水热污泥):70%(褐煤)与50%(水热污泥):50%(褐煤)为宜。 相似文献
722.
Marta Chrzanowska Anna Kozakiewicz Ralph Puchta 《Journal of Coordination Chemistry》2018,71(11-13):1761-1777
AbstractThe substitution behavior of the [RuII(terpy)(ampy)Cl]Cl (terpy = 2,2′:6′,2′′-terpyridine, ampy = 2-(aminomethyl)pyridine) complex in water with several bio-relevant ligands such as chloride, thiourea and N,N′-dimethylthiourea, was investigated and compared with the reactivity of the [RuII(terpy)(bipy)Cl]Cl and [RuII(terpy)(en)Cl]Cl (bipy =2,2′-bipyridine and en?=?ethylenediamine) complexes. Earlier results have shown that the reactivity and pKa values of Ru(II) complexes can be tuned by a systematic variation of electronic effects provided by bidentate spectator chelates. The reactivity of both the chlorido and aqua derivatives of the studied Ru(II) complexes increases in the order [RuII(terpy)(bipy)X]+/2+?<?[RuII(terpy)(ampy)X]+/2+?<?[RuII(terpy)(en)X]+/2+. This finding can be accounted for in terms of π back-bonding effects provided by the pyridine ligands. The activation parameters for all the studied reactions support an associative interchange substitution mechanism. 相似文献
723.
合成并表征了含RCOO-基团的单核(Ni1~Ni2)及双核(Ni3)镍配合物[(2,6-R2-C6H3)—N=C(H)—(3-Ph-5-PhCOO-2-O-C6H2)-κ2-N,O]Ni(CH3)(pyridine)](R=iPr;3,5-tBu2C6H3),并用于催化乙烯均聚和共聚反应。 作为单组分催化剂,这些配合物可以有效地催化乙烯聚合得到中等相对分子质量的支化聚乙烯(PE)。 供电性的PhCOO—基团促进了催化剂Ni1的引发,从而在低温下比Ni0活性更高。 引入大位阻的2,6-(3,5-二叔丁基苯基)苯胺基团,催化剂Ni2在5×105 Pa下的活性高达1.8×106 g PE mol-1·Ni-1·h-1,是活性最高的水杨醛亚胺中性镍催化剂之一。 与相应的单核催化剂相比,双核催化剂Ni3对三苯基膦具有更好的耐受性。 这些催化剂可催化乙烯与1,5-己二烯、1,7-辛二烯、6-溴-1-己烯或10-十一烯酸甲酯的共聚合,制备功能化聚乙烯。 相似文献
724.
In this review, oxygen activation and their aerobic oxidation over the Au nanoclusters are presented. The size-specificity, ligand engineering, and doping effects and the proposed reactions’ mechanism and the structure-activity relationships at the atomic level are also discussed. 相似文献
725.
Solvent‐Mediated Functionalization of Benzofuroxan on Electron‐Rich Ruthenium Complex Platform 下载免费PDF全文
Dr. Prabir Ghosh Sanchaita Dey Sanjib Panda Prof. Goutam Kumar Lahiri 《化学:亚洲杂志》2018,13(12):1582-1593
An unprecedented reactivity profile of biochemically relevant R‐benzofuroxan (R=H, Me, Cl), with high structural diversity and molecular complexity on a selective {Ru(acac)2} (acac=acetylacetonate) platform, in conjugation with EtOH solvent mediation, is revealed. This led to the development of monomeric [RuIII(acac)2(L1R)] ( 1 a – 1 c ; L1R=2‐nitrosoanilido derivatives) and dimeric [{RuII(acac)2}2(L2R)] ( 2 a – 2 b ; L2R=(1E,2E)‐N1,N2‐bis(2‐nitrosophenyl)ethane‐1,2‐diimine derivatives) complexes in one pot with a change in the metal redox conditions. The functionalization of benzofuroxan in 1 and 2 implied in situ reduction of N=O to NH? in the former and solvent‐assisted multiple N?C coupling in the latter. The aforesaid transformation processes were authenticated through structural elucidation of representative complexes, and evaluated by their spectroscopic/electrochemical features, along with C2D5OD labeling and monitoring of the impact of substituents (R) in the benzofuroxan framework on the product distribution process. The noninnocent potential of newly developed L1 and L2 in 1 and 2 , respectively, was also probed by spectroelectrochemistry in combination with DFT calculations. 相似文献
726.
5,12‐Diacetyl‐5,12‐dihydroquinoxalino[2,3‐b]quinoxalines: Solid‐State Fluorescence,AIE Properties,and Orbital Switching by Substituent Effect 下载免费PDF全文
The compound 5,12‐diacetyl‐5,12‐dihydroquinoxalino[2,3‐b]quinoxaline 1 a and its derivatives were prepared, and their solid‐ and solution‐state spectroscopic properties were studied; 1 a shows stronger fluorescence in solution than in the solid state due to aggregation caused by self‐quenching. Phenyl‐ or alkoxy‐substituted derivatives 1 b – d show solid‐state fluorescence with moderate quantum yields of about Φ=0.12–0.15, although the corresponding values are 0.01–0.07 in solution. The spectroscopic properties of alkoxy‐substituted derivatives were hardly changed compared to 1 a and 1 b , although 1 a and 1 b have similar absorption and fluorescence maxima in solution and in the solid state. DFT calculations indicate that orbital switching occurs between HOMO and HOMO‐1 and HOMO‐2 due to orbital interactions with introduced substituents. Crystal structure analysis revealed that the molecules have bent structures around tertiary nitrogen atoms and form a characteristic dimeric structure. 相似文献
727.
Marzieh Haghverdi Naeimeh Bahri-Laleh Mehdi Nekoomanesh Haghighi 《Journal of Coordination Chemistry》2018,71(8):1180-1192
Five 2-(1H-benzimidazol-2-yl)-phenol derivatives including 1H (HL1), 5-chloro-(HL2), 5-methyl-(HL3), 5,6-dichloro-(HL4), and 5,6-dimethyl-(HL5) were synthesized by the reaction of their corresponding benzene-1,2-diamine precursors and 2-hydroxybenzaldehyde which subsequently was employed in complexation with Fe(II) to prepare complexes C1–C5, respectively. Indeed, in all complexes, the ligands were coordinated as bidentate, via the C=N nitrogen and hydroxy oxygen atom of benzimidazole moiety and phenol ring, respectively. The compounds were characterized by FTIR, UV–vis, 1H- and 13C-NMR spectropscopy, ICP, and elemental analysis (C, H, and N). The purity of these compounds was determined by melting point (m.p )and TLC. The synthesized ligands and complexes were geometrically optimized by Gaussian09 software at B3LYP/TZVP level of theory and satisfactory theoretical–experimental agreement was achieved for analysis of IR data of the compounds. Catalytic behavior of the iron(II) complexes was investigated for ethylene reactivity. On activation with diethylaluminum chloride (Et2AlCl), iron(II) complex (C4) showed the highest activity (1686 kg oligomers.mol?1(Fe).h?1) for ethylene oligomerization when it contains chlorine substituents and exhibits good selectivity for linear 1-butene. The steric and electronic effects of ligands were investigated in detail on the influence of their catalytic activities. 相似文献
728.
The Ideal Ionic Liquid Salt Bridge for the Direct Determination of Gibbs Energies of Transfer of Single Ions,Part I: The Concept 下载免费PDF全文
Dr. Valentin Radtke Andreas Ermantraut Dr. Daniel Himmel Prof. Thorsten Koslowski Prof. Ivo Leito Prof. Ingo Krossing 《Angewandte Chemie (International ed. in English)》2018,57(9):2344-2347
Described is a procedure for the thermodynamically rigorous, experimental determination of the Gibbs energy of transfer of single ions between solvents. The method is based on potential difference measurements between two electrochemical half cells with different solvents connected by an ideal ionic liquid salt bridge (ILSB). Discussed are the specific requirements for the IL with regard to the procedure, thus ensuring that the liquid junction potentials (LJP) at both ends of the ILSB are mostly canceled. The remaining parts of the LJPs can be determined by separate electromotive force measurements. No extra‐thermodynamic assumptions are necessary for this procedure. The accuracy of the measurements depends, amongst others, on the ideality of the IL used, as shown in our companion paper Part II. 相似文献
729.
Interrupted Baeyer–Villiger Rearrangement: Building A Stereoelectronic Trap for the Criegee Intermediate 下载免费PDF全文
Dr. Vera A. Vil' Gabriel dos Passos Gomes Oleg V. Bityukov Prof. Konstantin A. Lyssenko Prof. Gennady I. Nikishin Prof. Igor V. Alabugin Prof. Alexander O. Terent'ev 《Angewandte Chemie (International ed. in English)》2018,57(13):3372-3376
The instability of hydroxy peroxyesters, the elusive Criegee intermediates of the Baeyer–Villiger rearrangement, can be alleviated by selective deactivation of the stereoelectronic effects that promote the 1,2‐alkyl shift. Stable cyclic Criegee intermediates constrained within a five‐membered ring can be prepared by mild reduction of the respective hydroperoxy peroxyesters (β‐hydroperoxy‐β‐peroxylactones) which were formed in high yields in reaction of β‐ketoesters with BF3?Et2O/H2O2. 相似文献
730.
Solvent‐Dependent Asymmetric Synthesis of Alkynyl and Monofluoroalkenyl Isoindolinones by CpRhIII‐Catalyzed C−H Activation 下载免费PDF全文
Teng Li Chao Zhou Xiaoqiang Yan Prof. Dr. Jun Wang 《Angewandte Chemie (International ed. in English)》2018,57(15):4048-4052
The asymmetric synthesis of alkynyl and monofluoroalkenyl isoindolinones from N‐methoxy benzamides and α,α‐difluoromethylene alkynes is enabled by C?H activation with a chiral CpRhIII catalyst. Remarkably, product formation is solvent‐dependent; alkynyl isoindolinones are afforded in MeOH (up to 86 % yield, 99.6 % ee) whereas monofluoroalkenyl isoindolinones are generated in iPrCN (up to 98:2 Z/E, 93 % yield, 86 % ee). Mechanistic studies revealed chiral allene and E‐configured alkenyl rhodium species as reaction intermediates. The latter is transformed into the corresponding Z‐configured monofluoroalkene upon protonation in the iPrCN system and into an alkyne by an unusual anti β‐F elimination in the MeOH system. Notably, kinetic resolution processes occur in this reaction. Despite the moderate enantiocontrol for the formation of the chiral allene, the Z‐monofluoroalkenyl isoindolinones and alkynyl isoindolinones were obtained in good enantiopurities by one or two sequential kinetic resolution processes. 相似文献