Spectroscopic study on the interaction between[Hg（SCN）4]2- and hemoglobin

The interaction between[Hg（SCN）₄]^2- and hemoglobin（Hb） under conditions that simulate a physiological environment was investigated by UV-vis spectroscopy,fluorescence spectroscopy,resonance Rayleigh scattering（RRS） spectroscopy and circular dichroism（CD） spectroscopy.The results obtained from the change of UV-vis and CD spectra,the quenching of Hb fluorescence and the enhancement of RRS intensity proved that a 10:1 type complex was formed between[Hg（SCN）₄]^2- and Hb.The possible mechanism suggested for the interaction was that ten Hg（SCN）₄]^2- anions entered the four subunits of a Hb molecule to react with some residues to form an adduct by coordination and electrostatic forces.The coordination of[Hg（SCN）₄]^2- with Trp was the major cause of the fluorescence quenching of Hb.     

ZrOCl2·8H2O catalyzed solvent-free synthesis of isobenzofuran-1（3H）-ones

ZrOCl₂·8H₂O catalyzed environmentally benign synthesis of isobenzofuran-1（3H）-ones are described.ZrOCl₂·8H₂O appeared to be an excellent catalyst for the condensation and reactions.Reaction of phthalaldehydic acid（2-carboxybenzaldehyde） with methylaryl and cyclic ketones was initiated by condensation and occurred in one step providing excellent yields（90-98%）.     

KAl（SO4）2·12H2O catalyzed efficient synthesis of 3,4,6-trisubstituted 2-pyridone in water

An efficient green protocol for the preparation 3,4,6-trisubstituted 2-pyridone of employing a condensation reaction of cyanoacetamide and acetylacetone in the presence of KAl（SO₄）₂·12H₂O in water has been described.The present procedure offers advantage such as shorter reaction time,simple workup,and excellent yields.     

Noncentrosymmetric K2Mn3(SO4)3F2·4H2O and Rb2Mn3(SO4)3F2·2H2O with pseudo-KTP structures

Two fluoride sulfates,K₂Mn₃(SO₄)₃F₂·4H₂O(Ⅰ) and Rb₂Mn₃(SO₄)₃F₂·2H₂O (Ⅱ) are obtained by water solution method.Single-crystal X-ray diffraction analysis indicated that they crystallize in space groups of Cmc2_1.Their structures feature a pseudo-KTP structure consisting of interconnecting[Mn₃(SO₄)3F₂(H₂O)2]_∞ layers,which are further packing along the a axis with alkali metal cations balancing the charges.The structure relationships between the two compounds are discussed.Secondharmonic generation measurements manifest that Ⅰ and Ⅱ have similar second-harmonic generation responses of about 0.2 and 0.25 times that of KH₂PO₄.     

First-principles characterization of formate and carboxyl adsorption on stoichiometric CeO2（111）and CeO2（110） surfaces

Molecular adsorption of formate and carboxyl on stoichiometric CeO₂（111） and CeO₂（110） surfaces was studied using periodic density functional theory（DFT+U） calculations.Two distinguishable adsorption modes（strong and weak） of formate are identified.The bidentate configuration is more stable than the monodentate adsorption configuration.Both formate and carboxyl bind at the more open CeO₂（110） surface are stronger.The calculated vibrational frequencies of two adsorbed species are consistent with the experimental measurements.Finally, the effects of U parameters on the adsorption of formate and carboxyl over both CeO₂ surfaces were investigated.We found that the geometrical configurations of two adsorbed species are not affected by different U parameters（U=0,5,and 7）.However,the calculated adsorption energy of carboxyl pronouncedly increases with the U value while the adsorption energy of formate only slightly changes（<0.2 eV）. The Bader charge analysis shows the opposite charge transfer occurs for formate and carboxyl adsorption where the adsorbed formate is negatively charge while the adsorbed carboxyl is positively charged.Interestingly,with the increasing U parameter,the amount of charge is also increased.     

Highly efficient photocatalytic NO removal and in situ DRIFTS investigation on SrSn（OH）6

A novel SrSn（OH）₆ photocatalyst with large plate and particle size were synthesized via a facile chemical precipitation method.The photocatalytic activity of the SrSn（OH）₆ was evaluated by the removal of NO at ppb level under UV light irradiation.Based on the ESR measurements,SrSn（OH）₆ photocatalyst was found to have the ability to generate the main active species of O₂^·-,^·OH and ¹ O₂ during the photocatalyti...     

Electrocatalytic construction of the C–N bond from the derivates of CO2 and N2

Electrochemical synthesis of C-N bond-containing compounds(e.g.,urea,amino acid,amide,amine,and their derivates)from CO₂/N₂and their derivates is emerging as a promising sustainable strategy[1-7].CO₂and its derived products,CO,HCOOH,(COOH)₂,etc.,could serve as carbon sources(Figure 1)[8].N₂,making up 80%of air,is an appealing nitrogen source.However,the low solubility of N2 and the high dissociation energy for the N≡N bond limit its application.     

载体ZrO2的d带电子对Ni13催化CH4脱氢过程的影响（英文）

C-H键活化是甲烷转化的关键，分散于ZrO₂（111）表面的活性Ni₁₃微粒能实现这一过程。密度泛函理论结果表明，相比Ni₁₃催化过程，Ni₁₃-ZrO₂（111）更能活化CH₄逐步脱氢并稳定其解离物种；且在载体ZrO₂存在下，C-H键长增加，C-H断键活化能降低，放热量增多，达过渡态时，解离H与残留CH_x间距减小，因此，负载催化剂Ni₁₃-ZrO₂（111）具有更好的催化性。究其原因，对于Ni-C-H,ZrO₂丰富的d带电子使得Ni 3d电子密度增强，C 2p与Ni 3d轨道重叠增多，Ni-C键增强，C-H键减弱，基于此，CH_x吸附增强，C-H键活性亦增强。因此，载体ZrO₂的d带为Ni₁₃活化CH₄促进C-H键解离提供着电子。     

A copper-catalyzed three-component reaction of alkenes,cycloketone oximes and DABCO·（SO2）2: Direct C（sp2）-H cyanoalkylsulfonylation

A copper-catalyzed three-component reaction of alkenes, cycloketone oximes and DABCO·（SO₂）₂ is developed, which provides a convenient route for the synthesis of diverse（E）-cyanoalkylsulfonyl alkenes in moderate to good yields with excellent regio-and stereoselectivity. A broad substrate scope with excellent functional group tolerance is observed. A plausible radical pathway is proposed, which involves copper-catalyzed ring-opening C–C bond cleavage of O-acyl oxime and inser...     

Catalytic conjugate addition of indole toα,β-unsaturated ketones by Co（ClO4）-2·6H2O/bis-Schiff base complexes

Co（ClO₄）)₂·6H₂O/bis-Schiff base complexes promoted the conjugate addition of indole toα,β-unsaturated ketones under mild conditions,giving the corresponding addition products with high yields.And the complex has been characterized with XRD and IR.     

Visible-light deposition of CrOx cocatalyst on TiO2:Cr valence regulation for superior photocatalytic CO2reduction to CH4

Photodeposition is widely adopted for implanting metal/metal oxide cocatalysts on semiconductors.However,it is prerequisite that the photon energy should be sufficient to excite the host semiconductor.Here,we report a lower-energy irradiation powered deposition strategy for implanting CrO_x cocatalyst on TiO₂.Excitingly,CrO_x-400 implanted under visible-light irradiation significantly promotes the CH4 evolution rate on TiO₂to 8.4μmolg·^-1h^-1 with selectivity of98%from photocatalytic CO₂reduction,which is 15 times of that on CrO_x-200 implanted under UV-visible-light irradiation.Moreover,CrO_x-400 is identified to be composed of higher valence Cr species compared to CrO_x-200.This valence states regulation of Cr species is indicated to provide more active sites for CO₂ adsorption/activation and to modulate the reaction mechanism from single Cr site to Cr-Cr dual sites,thus endowing the superior CH₄production.This work demonstrates an alternative strategy for constructing efficient metal oxides cocatalysts on wide bandgap semiconductor.     

Bi and S Co-doping g-C3N4 to Enhance Internal Electric Field for Robust Photocatalytic Degradation and H2 Production

By adjusting the type and proportion of doping elements in the g-C₃N₄-based photocatalyst, the internal electric field（IEF） strength of the semiconductor can be regulated. This can effectively enhance the driving force of charge separation in the photocatalytic process. It is found that the introduction of appropriate concentration of Bi and S into the skeleton structure of g-C₃N₄ can achieve efficient degradation of tetracycline（TC） and other pollutan...     

Progress and Understanding on Catalysts with Well-defined Interface for Boosting CO2 Conversion

Catalytic conversion of CO₂ into valuable chemicals like CH₃OH is the most promising way to alleviate CO₂ emission for solving the serious climate change issue. Multi-component catalysts with well-defined interface show outstanding performance in CO₂ conversion due to the synergistic effects and multifunctional properties caused by the well-defined interface. A discharge technique, named as cold plasma, has been recognized as an excellent strategy for ...     

Synthesis,Characterization, and DNA Binding Properties of Dinuclear Copper（Ⅱ） Complex [Cu2（TATP）2（L-Leu）2（CIO4）2]2·2H2O

A dinuclear copper（Ⅱ） complex[Cu2（TATP）2（L-Leu）2（CIO4）2]2·2H2Owas synthesized and characterized, where, TATP=1,4,8,9-tetraazatriphenylene, and L-Leu=L-leucinate. The complex was crystallized in the triclinic space group P1, with two independent molecules in a unit cell. Two Cu（Ⅱ） ions in each complex [Cu2（TATP）2（L-Leu）2（CIO4）2] molecule were found to be in different coordination geometries, i.e., Cu2 or Cu4 of a distorted square-pyramidal geometry coordinated with two nitrogens of TATP, the amino nitrogen and one carboxylate oxygen of L-Leu and one oxygen of perchlorate, and Cul or Cu3 with an octahedral geometry coordinated with the above stated similar coordinated atoms, and another carboxylate oxygen of L-Leu coordinating to Cu2 or Cu4. The complex can interact with CT-DNA by an intercalative mode and cleave pBR322 DNA in the presence of ascorbate.     

Influence of Pd deposition pH value on the performance of Pd-CuO/SiO2 catalyst for semi-hydrogenation of 2-methyl-3-butyn-2-ol（MBY）

The selective hydrogenation of C≡C to C=C bonds is an important step, yet remains to be a great challenge in chemical industry. In this study, we have revealed the influence of Pd deposition pH value on the catalytic performance of Pd-CuO/SiO₂ catalyst for the semi-hydrogenation of 2-methyl-3-butyn-2-ol（MBY）. Trace amount of Pd（about 500 ppm） was loaded via deposition-reduction method on CuO/SiO₂ support by using H₂PdCl₄ solution as precursor and NaBH<...     

Two Alkali Metal Germanophosphates Na3[Ge(OH)(PO4)2]·2H2O and Li2Na[GeO(HPO4)(PO4)]:Crystal Structures and Thermal Stability

Two new alkali metal germanophosphates,namely,Na₃[Ge(OH)(PO₄)₂]·2 H2 O and Li₂Na[GeO(HPO₄)(PO₄)],have been prepared by solvothermal method,and their crystal structures were determined by single-crystal X-ray diffraction.The title two compounds crystalize in the same orthorhombic space group Pbcm(No.57)and feature similar chain-like structure which is built from zig-zag GeO₆ octahedral thread loop branched by PO₄ tetrahedra.For Na₃[Ge(OH)(PO₄)₂]·2 H₂O,a=10.1650(9),b=13.1975(12),c=6.9751(7)?,V=935.73(15)?³,Z=4,R=0.0356 and wR=0.1109;and for Li₂Na[GeO(HPO₄)(PO₄)],a=6.9855(5),b=14.5809(18),c=6.6620(5)?,V=678.56(11)?³,Z=4,R=0.0286,and w R=0.0762.The partial substitution of Na ions by Li ions not only significantly influences the total structural features and the water molecule contents,but also impacts on their thermal stabilities.Li₂Na[GeO(HPO₄)(PO₄)]is thermally stable up to 400℃,whereas only 150℃ for Na₃[Ge(OH)(PO₄)₂]·2 H2 O.     

Ag2S Quantum Dots Decorated on Porous Cubic-CdS Nanosheets-assembled Flowers for Photocatalytic CO2 Reduction

The production of renewable fossil fuels such as CH₄ and CO by photocatalytic CO₂ reduction has attracted more and more attention. However, single photocatalyst is less efficient for photocatalytic reduction of CO₂ due to the fast recombination of photogenerated electron pairs. Herein, we successfully prepare Cd S-Ag₂S composite by assembling the Ag₂S QDs cocatalyst on the surface of Cd S nanosheet-assembled flower through oil-bath solvother...     

反应条件对Ni-CaO-ZrO2催化剂上CH4-CO2重整反应及积炭的影响

用共沉淀法制备了Ni-CaO-ZrO₂催化剂,并将其用于CH₄-CO₂重整反应。考察了反应温度、空速和反应物配比对催化剂性能和积炭的影响。通过热力学计算和实验表征研究发现,反应条件对CH₄-CO₂重整反应结果和积炭有重要的影响。由于高温条件同时有利于CH₄裂解和碳物种的及时消除,升高温度可以提高催化剂的活性和稳定性。增大空速则使CH₄的转化率和消碳反应的速率均降低,导致积炭量增加。同时,反应物配比对催化剂表面的积炭量也有很大影响;稍高的CO₂/CH₄摩尔比有利于抑制CH₄-CO₂重整反应过程中的积炭。     

光催化CO2还原为CH4研究进展(英文)

太阳能驱动二氧化碳光催化还原为CH₄是缓解全球变暖和能源危机的有效策略,然而,光催化效率较低以及产物选择性差,严重阻碍其大规模商业化应用。探究光催化CO₂还原反应机理对解决以上问题有重要参考意义,因此本文对光催化CO₂还原为C₁产物的基本原理及路径进行阐述,主要综述提高CO₂光还原效率以及CH₄选择性的方法,如构建异质结、设计结构缺陷、引入单原子催化剂以及其他方法,最后指出CO₂光还原CH₄面临的挑战和发展前景。     

The role of NiFe2O4 nanoparticle in the anaerobic digestion（AD） of waste activated sludge（WAS）

Anaerobic digestion（AD） is a promising technology for the treatment of waste activated sludge（WAS）with energy recovery. However, the low methane yield and slow methanogenesis limit its broad application. In this study, the NiFe₂O₄ nanoparticles（NPs） were fabricated and applied as a conductive material to enhance the AD via promoting the direct interspecies electron transfer（DIET）. The crystal structure,specific surface area, morphology and elemental composition of the as-pr...