Size-complementary effects of PEG diamine 1,1’-disubstituted ferrocene on incorporations of β- and γ-cyclodextrins and syntheses of poly(pseudo)rotaxanes with lower coverages therefrom

Journal of Inclusion Phenomena and Macrocyclic Chemistry - Poly(ethylene glycol) diamine 1,1’-disubstituted ferrocene was utilized as a size-com-plementary site to synthesize lower coverage...     

Manipulating Electric Double Layer Adsorption for Stable Solid-Electrolyte Interphase in 2.3 Ah Zn-Pouch Cells

Constructing a reliable solid-electrolyte interphase (SEI) is imperative for enabling highly reversible zinc metal (Zn⁰) electrodes. Contrary to conventional “bulk solvation” mechanism, we found the SEI structure is dominated by electric double layer (EDL) adsorption. We manipulate the EDL adsorption and Zn²⁺ solvation with ether additives (i.e. 15-crown-5, 12-crown-4, and triglyme). The 12-crown-4 with medium adsorption on EDL leads to a layer-structured SEI with inner inorganic ZnF_x/ZnS_x and outer organic C−O−C components. This structure endows SEI with high rigidness and strong toughness enabling the 100 cm² Zn||Zn pouch cell to exhibit a cumulative capacity of 4250 mAh cm⁻² at areal-capacity of 10 mAh cm⁻². More importantly, a 2.3 Ah Zn||Zn_0.25V₂O₅⋅n H₂O pouch cell delivers a recorded energy density of 104 Wh L_cell⁻¹ and runs for >70 days under the harsh conditions of low negative/positive electrode ratio (2.2 : 1), lean electrolyte (8 g Ah⁻¹), and high-areal-capacity (≈13 mAh cm⁻²).     

Alloying-Triggered Phase Engineering of NiFe System via Laser-Assisted Al Incorporation for Full Water Splitting

It is challenging to design one non-noble material with balanced bifunctional performance for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) for commercial sustainability at a low cost since the different electrocatalytic mechanisms are not easily matchable for each other. Herein, a self-standing hybrid system Ni₁₈Fe₁₂Al₇₀, consisting of Ni₂Al₃ and Ni₃Fe phases, was constructed by laser-assisted aluminum (Al) incorporation towards full water splitting. It was found that the incorporation of Al could effectively tune the morphologies, compositions and phases. The results indicate that Ni₁₈Fe₁₂Al₇₀ delivers an extremely low overpotential to trigger both HER (η₁₀₀=188 mV) and OER (η₁₀₀=345 mV) processes and maintains a stable overpotential for 100 h, comparable to state-of-the-art electrocatalysts. The synergistic effect of Ni₂Al₃ and Ni₃Fe alloys on the HER process is confirmed based on theoretical calculation.     

Combining Deep Eutectic Solvents with TEMPO-based Polymer Electrodes: Influence of Molar Ratio on Electrode Performance**

For sustainable energy storage, all-organic batteries based on redox-active polymers promise to become an alternative to lithium ion batteries. Yet, polymers contribute to the goal of an all-organic cell as electrodes or as solid electrolytes. Here, we replace the electrolyte with a deep eutectic solvent (DES) composed of sodium bis(trifluoromethanesulfonyl)imide (NaTFSI) and N-methylacetamide (NMA), while using poly(2,2,6,6-tetramethylpiperidin-1-yl-oxyl methacrylate) (PTMA) as cathode. The successful combination of a DES with a polymer electrode is reported here for the first time. The electrochemical stability of PTMA electrodes in the DES at the eutectic molar ratio of 1 : 6 is comparable to conventional battery electrolytes. More viscous electrolytes with higher salt concentration can hinder cycling at high rates. Lower salt concentration leads to decreasing capacities and faster decomposition. The eutectic mixture of 1 : 6 is best suited uniting high stability and moderate viscosity.     

Bioinspired Design of a Giant [Mn86] Nanocage-Based Metal-Organic Framework with Specific CO2 Binding Pockets for Highly Selective CO2 Separation

Adsorption-based removal of carbon dioxide (CO₂) from gas mixtures has demonstrated great potential for solving energy security and environmental sustainability challenges. However, due to similar physicochemical properties between CO₂ and other gases as well as the co-adsorption behavior, the selectivity of CO₂ is severely limited in currently reported CO₂-selective sorbents. To address the challenge, we create a bioinspired design strategy and report a robust, microporous metal–organic framework (MOF) with unprecedented [Mn₈₆] nanocages. Attributed to the existence of unique enzyme-like confined pockets, strong coordination interactions and dipole-dipole interactions are generated for CO₂ molecules, resulting in only CO₂ molecules fitting in the pocket while other gas molecules are prohibited. Thus, this MOF can selectively remove CO₂ from various gas mixtures and show record-high selectivities of CO₂/CH₄ and CO₂/N₂ mixtures. Highly efficient CO₂/C₂H₂, CO₂/CH₄, and CO₂/N₂ separations are achieved, as verified by experimental breakthrough tests. This work paves a new avenue for the fabrication of adsorbents with high CO₂ selectivity and provides important guidance for designing highly effective adsorbents for gas separation.     

Selective Encapsulation and Chiral Induction of C60 and C70 Fullerenes by Axially Chiral Porous Aromatic Cages

Chiral induction has been an important topic in chemistry, not only for its relevance in understanding the mysterious phenomenon of spontaneous symmetry breaking in nature but also due to its critical implications in medicine and the chiral industry. The induced chirality of fullerenes by host–guest interactions has been rarely reported, mainly attributed to their chiral resistance from high symmetry and challenges in their accessibility. Herein, we report two new pairs of chiral porous aromatic cages (PAC), R- PAC-2 , S- PAC-2 (with Br substituents) and R- PAC-3 , S- PAC-3 (with CH₃ substituents) enantiomers. PAC-2 , rather than PAC-3 , achieves fullerene encapsulation and selective binding of C₇₀ over C₆₀ in fullerene carbon soot. More significantly, the occurrence of chiral induction between R- PAC-2 , S- PAC-2 and fullerenes is confirmed by single-crystal X-ray diffraction and the intense CD signal within the absorption region of fullerenes. DFT calculations reveal the contribution of electrostatic effects originating from face-to-face arene-fullerene interactions dominate C₇₀ selectivity and elucidate the substituent effect on fullerene encapsulation. The disturbance from the differential interactions between fullerene and surrounding chiral cages on the intrinsic highly symmetric electronic structure of fullerene could be the primary reason accounting for the induced chirality of fullerene.     

Stereoselective Synthesis of Enamides through Palladium-Catalyzed Oxidative Amidation of Conjugated Olefins with 2-Pyridones

A palladium-catalyzed oxidative amidation of conjugated olefin with 2-pyridone is described. A series of E-Enamides were synthesized in a highly stereocontrolled manner. The reaction also accommodates other cyclic and acyclic amides. Z-Enamides were predominantly prepared for primary amides probably due to the presence of an intramolecular hydrogen bond. Gram-scale synthesis of enamide and the following oxidative annulation with diphenylacetylene demonstrates the synthetic utility of this reaction.     

Simple high-performance liquid chromatography-ultraviolet method for simultaneous separation and detection of 14 bisphenol pollutants in building materials

A high-performance liquid chromatography-ultraviolet method was developed for rapidly and simultaneously analyzing novel and typical bisphenols in building materials, including bisphenol S, diphenolic acid, bisphenol F, bisphenol E, bisphenol A, bisphenol B, bisphenol AF, bisphenol AP, bisphenol C, bisphenol FL, bisphenol Z, bisphenol BP, bisphenol M, and bisphenol P. By using a Kromasil 100–5 C18 column, these bisphenols were completely separated in 40 min via gradually increasing the concentration of methanol in the mobile phase from 45 to 80% during the elution process. In particular, this method achieved the synchronous analysis of bisphenol S, diphenolic acid, bisphenol FL, bisphenol BP, and bisphenol M through HPLC, which were difficult to separate and had to be identified and detected through mass spectrometry. The limits of detection of the method ranged from 0.002 to 0.040 mg/L for these 14 bisphenols, with a precision of less than 4.9% (n = 7, c = 0.05 mg/L). The analytical results for five types of building materials (phenolic, epoxy, polycarbonate, polyester, and polysulfone resins) indicated that the proposed method is appropriated for the rapid measurement of bisphenols in real samples.     

Probing Bis‐FeIV MauG: Experimental Evidence for the Long‐Range Charge‐Resonance Model

The biosynthesis of tryptophan tryptophylquinone, a protein‐derived cofactor, involves a long‐range reaction mediated by a bis‐Fe^IV intermediate of a diheme enzyme, MauG. Recently, a unique charge‐resonance (CR) phenomenon was discovered in this intermediate, and a biological, long‐distance CR model was proposed. This model suggests that the chemical nature of the bis‐Fe^IV species is not as simple as it appears; rather, it is composed of a collection of resonance structures in a dynamic equilibrium. Here, we experimentally evaluated the proposed CR model by introducing small molecules to, and measuring the temperature dependence of, bis‐Fe^IV MauG. Spectroscopic evidence was presented to demonstrate that the selected compounds increase the decay rate of the bis‐Fe^IV species by disrupting the equilibrium of the resonance structures that constitutes the proposed CR model. The results support this new CR model and bring a fresh concept to the classical CR theory.     

氧化钛负载脱硝催化剂的碱中毒过程：氧化钒的保留和氧化钨的牺牲

V2O5-WO3/TiO2催化剂目前已广泛用于电厂和工业锅炉燃烧废气脱硝,但燃烧原料煤及石油中含有的杂质元素碱金属与碱土金属元素可吸附在催化剂上,不仅会减少催化剂酸性位的数量,还会与催化活性元素结合生成惰性物种,导致催化剂失活。因此,已有许多有关钒钨钛催化剂碱中毒的研究,从催化剂的氧化还原能力、酸性位损失及表面孔结构等方面进行了讨论。但这些研究大多集中在碱中毒对活性组分V2O5的影响及中毒催化剂的活性变化,很少涉及催化剂中WO3的作用,也缺乏有关不同活性元素与钾盐反应的实验证据。本文采用过量浸渍法制备了不同钒和钨含量的钒钨钛催化剂,研究了氯化钾对其氨法选择性催化还原(NH3-SCR)活性的失活效应。利用感应耦合等离子体、N2吸附、拉曼光谱、H2程序升温还原、NH3吸附红外光谱和NH3氧化活性等手段对新鲜和中毒催化剂的性质进行了表征,特别探讨了V2O5和WO3对催化剂抗碱中毒能力的贡献。
　　催化剂活性测试结果表明, V2O5含量越高,活性温度窗口越宽,而且含有WO3的三元催化剂活性高于V2O5/TiO2二元催化剂。催化剂的BET比表面积和孔结构取决于TiO2载体,随活性组分配比变化不大,说明催化剂物理结构性质并非影响活性的主要因素。原位红外光谱及H2程序升温还原测试结果表明,随V2O5含量提高,催化剂表面Br?nsted酸性位数量及氧化还原能力提高。作为反应的主要活性物种, V2O5在碱中毒处理后变成惰性的偏钒酸钾KVO3,使催化剂中Br?nsted酸性位减少,热稳定性下降,并削弱了催化剂的氧化还原能力,因此低钒含量的催化剂容易严重中毒失活。在高钒负载量(3%)时,部分V2O5在碱中毒后得以保留,从而使催化剂保持了一定的脱硝催化活性。
　　另外, WO3能给催化剂表面提供热稳定的酸性位,虽然WO3自身的氧化还原能力差,但其能改善V2O5的分散性,从而提高V2O5-WO3/TiO2催化剂的活性。除此之外, WO3在催化剂碱中毒过程中还能扮演牺牲剂,与钾反应生成钨酸钾(K2WO4),即在V2O5与钾离子结合形成KVO3的同时,部分WO3也会与钾反应形成K2WO4,可以使三元催化剂保留更多的活性V物种。因此,在所研究的催化剂中,高钒负载量的V2O5-WO3/TiO2催化剂表现出最好的抗碱中毒能力。
　　活性影响因素分析表明,对于新鲜催化剂,其表面吸附的NH3量足够多,催化剂活性与表面酸性相关度不大,脱硝效率主要取决于催化剂的氧化还原能力。但是,对于碱中毒处理后的催化剂,其表面吸附NH3的能力大大削弱,这时脱硝效率除了受催化剂氧化还原能力影响,在很大程度上也依赖于催化剂的表面酸性。