Carbon nitride with encapsulated nickel for semi-hydrogenation of acetylene: pyridinic nitrogen is responsible for hydrogen dissociative adsorption

A new mechanism of catalyst has been demonstrated in this article. With the interaction between carbon nitride (CN) and encapsulated nickel, the CN in the catalyst has been endowed with new active sites for the adsorption and activation of hydrogen while nickel itself is physically isolated from the contact with reactive molecules. For the selective hydrogenation of acetylene in large amount of ethylene, the catalyst shows excellent ethylene selectivity than the nickel catalyst itself, which is almost totally unselective. Meanwhile, the CN itself is inactive for the reaction. The results of characterization demonstrate that pyridinic nitrogen doped in the carbon matrix should be the active sites for hydrogen dissociative adsorption. The theoretical calculations further confirm the results and provide with the detail in the electron transfer between nickel and CN in the catalyst. The current results supply a new concept for design of high performance catalyst.     

A post curing strategy toward the feasible covalent adaptable networks in polyacrylate latex films

The implementation of covalent adaptable networks (CANs) in general resin system is becoming attractive. In this work, we propose a simple post-curing strategy based on the core-shell structured acrylate latex for the achievement on both the improved general performance and the CANs characteristics in latex films. The building to the CANs was relied on the introduction of 4,4′-diaminophenyl disulfide as the curing agent, which cured the acetoacetoxy decorated shell polymer through the ketoamine reaction. The metathesis reaction of aromatic disulfides in the crosslinking segments enabled the thermally induced dynamic behavior of the network as revealed in the stress relaxation tests by comparison with other diamine crosslinking agents without the incorporation of disulfide. The synergism of the dynamic crosslinking of the shell polymer and static crosslinking in the core polymer contributed to the improved mechanical strength (15 MPa, strain% = 250%) and the suppressed water adsorption (~1% in 24 h of soaking) of the latex film, which exhibited above 90% of recovery in both strength and strain from a cut-off film damage within 1 h at 80°C. Moreover, the cured latex film could be recycled, and 75% of the mechanical performance was regained after three fragmentation-hot-pressing cycles. These, in addition with the feasible and environmental friendly characteristics, suggest a sustainable paradigm toward the smart thermosetting latex polymers.     

沿海石化基地对地方生态环境补偿的科学基础与系统框架

生态文明建设既需要产业自身绿色发展,又需要利益调节,实现规模性达标排放行业与地方和谐.沿海石化基地既是中国能源与化学工业的集聚地,更是各类规模性达标三废集中排放区域,为此生态文明的地方实践要务就是推进石化基地对地方生态环境补偿.因此系统分析指导中国石化集聚区对地方生态补偿的外部性、公共物品、可持续发展、绿色GDP、博弈论等理论,构建宏观层次的生态环境补偿原则与补偿程序、中观层次的利益主体参与式的补偿运行机制,以及微观层次企业、居民、多层政府协商的生态环境补偿完善机制,并总结国内外实践经验,可以为地方践行生态文明理念、创新生态发展模式提供理论指导.     

CoMn@NC催化5-羟甲基糠醛常压氧化为2, 5-呋喃二甲酸二甲酯

Dimethyl furan-2, 5-dicarboxylate (DMFDCA) is a valuable biomass-derived chemical that is an ideal alternative to fossil-derived terephthalic acid as a monomer for polymers. The one-step oxidation of 5-hydroxymethylfurfural (HMF) to DMFDCA is of practical significance. It not only shortens the reaction pathway but also avoids the separation process of intermediates; thus, reducing cost. In this work, non-noble bimetallic catalysts supported on N-doped porous carbon (CoMn@NC) were synthesized via a one-step co-pyrolysis procedure using different pyrolysis temperatures and proportions of metal precursors and additives. We employed the prepared CoMn@NC catalysts in the aerobic oxidation of HMF under mild reaction conditions to obtain DMFDCA. High-yield DMFDCA was obtained by screening the prepared catalysts and optimizing the reaction conditions, including the strength and amount of the base, as well as the reaction temperature. The optimized yield of DMFDCA was 85% over the Co₃Mn₂@NC-800 catalyst after 12 h at 50 ℃ using ambient-pressure oxygen. The physicochemical properties of the catalysts were determined using a variety of characterization techniques, the factors affecting the performance of each catalyst were investigated, and the relationship between the physicochemical properties and performance of the prepared catalysts was elucidated. A porous structure with a high surface area had a positive effect on mass transfer efficiency. Cobalt nanoparticles (NPs) and atomically dispersed Mn were coordinated to N-doped carbon to form M―N_x (where M = Co or Mn). Based on the Mott-Schottky effect, there was significant electron transfer between each metal and the N-doped carbon, additionally, the metal NPs supplied electrons to the carbon atoms. The electron-deficient metal site in the pyridinic N-rich carbon was beneficial for the activation of HMF and oxygen. The activation of oxygen produced reactive oxygen species (such as superoxide radical anions) to ensure high selectivity to DMFDCA through dehydrogenative oxidation of the hemiacetal intermediate and hydroxymethyl group of 5-hydroxymethyl-2-methyl-furoate. The existence of disordered and defective carbons increased the number of active sites. Subsequently, we performed a series of control experiments. Based on our current experimental results and previous studies, we propose a simple mechanism for the aerobic oxidation of HMF to DMFDCA. The catalyst was stable, its performance decreased slightly after two cycles, and it was tolerant to SCN⁻ ions and resistant against N or S poisoning. Furthermore, the use of this catalytic system can be expanded to various substituted aromatic alcohols, such as benzyl alcohols with different substituents, furfuryl alcohol, and heterocyclic alcohols. Simultaneously, the product type was further extended from methyl esters to ethyl esters with a high yield when the substrate reacted with ethanol. In conclusion, this catalytic system can be applied in the production of carboxylic esters for polymers.     

Tuning the CO2 Hydrogenation Selectivity of Rhodium Single-Atom Catalysts on Zirconium Dioxide with Alkali Ions

Tuning the coordination environments of metal single atoms (M₁) in single-atom catalysts has shown large impacts on catalytic activity and stability but often barely on selectivity in thermocatalysis. Here, we report that simultaneously regulating both Rh₁ atoms and ZrO₂ support with alkali ions (e.g., Na) enables efficient switching of the reaction products from nearly 100 % CH₄ to above 99 % CO in CO₂ hydrogenation in a wide temperature range (240–440 °C) along with a record high activity of 9.4 mol_CO g_Rh⁻¹ h⁻¹ at 300 °C and long-term stability. In situ spectroscopic characterization and theoretical calculations unveil that alkali ions on ZrO₂ change the surface intermediate from formate to carboxy species during CO₂ activation, thus leading to exclusive CO formation. Meanwhile, alkali ions also reinforce the electronic Rh₁-support interactions, endowing the Rh₁ atoms more electron deficient, which improves the stability against sintering and inhibits deep hydrogenation of CO to CH₄.     

Giant Tunability of Charge Transport in 2D Inorganic Molecular Crystals by Pressure Engineering

The unique intermolecular van der Waals force in emerging two-dimensional inorganic molecular crystals (2DIMCs) endows them with highly tunable structures and properties upon applying external stimuli. Using high pressure to modulate the intermolecular bonding, here we reveal the highly tunable charge transport behavior in 2DIMCs for the first time, from an insulator to a semiconductor. As pressure increases, 2D α-Sb₂O₃ molecular crystal undergoes three isostructural transitions, and the intermolecular bonding enhances gradually, which results in a considerably decreased band gap by 25 % and a greatly enhanced charge transport. Impressively, the in situ resistivity measurement of the α-Sb₂O₃ flake shows a sharp drop by 5 orders of magnitude in 0–3.2 GPa. This work sheds new light on the manipulation of charge transport in 2DIMCs and is of great significance for promoting the fundamental understanding and potential applications of 2DIMCs in advanced modern technologies.     

Sodium Carbazolide and Derivatives as Solid-State Electrolytes for Sodium-Ion Batteries

Replacing widely used organic liquid electrolytes with solid-state electrolytes (SSEs) could effectively solve the safety issues in sodium-ion batteries. Efforts on seeking novel solid-state electrolytes have been continued for decades. However, issues about SSEs still exist, such as low ionic conductivity at ambient temperature, difficulty in manufacturing, low electrochemical stability, poor compatibility with electrodes, etc. Here, sodium carbazolide (Na-CZ) and its THF-coordinated derivatives are rationally fabricated as Na⁺ conductors, and two of their crystal structures are successfully solved. Among these materials, THF-coordinated complexes exhibit fast Na⁺ conductivities, i.e., 1.20×10⁻⁴ S cm⁻¹ and 1.95×10⁻³ S cm⁻¹ at 90 °C for Na-CZ-1THF and Na-CZ-2THF, respectively, which are among the top Na⁺ conductors under the same condition. Furthermore, stable Na plating/stripping is observed even over 400 h cycling, showing outstanding interfacial stability and compatibility against Na electrode. More advantages such as ease of synthesis, low-cost, and cold pressing for molding can be obtained. In situ NMR results revealed that the evaporation of THF may play an essential role in the Na⁺ migration, where the movement of THF creates defects/vacancies and facilitates the migration of Na⁺.     

The Two‐Step Assemblies of Basic‐Amino‐Acid‐Rich Peptide with a Highly Charged Polyoxometalate

Two‐step assembly of a peptide from HPV16 L1 with a highly charged europium‐substituted polyoxometalate (POM) cluster, accompanying a great luminescence enhancement of the inorganic polyanions, is reported. The mechanism is discussed in detail by analyzing the thermodynamic parameters from isothermal titration calorimetry (ITC), time‐resolved fluorescent and NMR spectra. By comparing the actions of the peptide analogues, a binding process and model are proposed accordingly. The driving forces in each binding step are clarified, and the initial POM aggregation, basic‐sequence and hydrophobic C termini of peptide are revealed to contribute essentially to the two‐step assembly. The present study demonstrates both a meaningful preparation for bioinorganic materials and a strategy using POMs to modulate the assembly of peptides and even proteins, which could be extended to other proteins and/or viruses by using peptides and POMs with similar properties.     

介质阻挡放电甲醇脱氢偶联一步合成乙二醇反应中氢气的催化作用

利用原位发射光谱表征和在线色谱分析,研究了甲醇介质阻挡放电脱氢偶联一步合成乙二醇反应中氢气的催化作用,考察了放电频率、甲醇和氢气进料量以及反应压力的影响.结果表明,在介质阻挡放电产生的非平衡等离子体中,H2不但能显著提高甲醇转化率,而且能显著提高乙二醇的选择性.在300°C,0.1 MPa,反应器注入功率为11 W,放电频率为12.0 k Hz,甲醇气体进料量为11.1 m L/min,氢气进料量为80–180 m L/min的条件下,甲醇转化率接近30%,乙二醇选择性大于75%.乙二醇收率与激发态氢原子的Hα谱线强度之间存在同增同减关系.由此推测,氢原子是起催化作用的活性氢物种.活性氢物种的生成途径是:基态氢分子通过与电子碰撞变成激发态,激发态氢分子通过第一激发态氢自动解离为基态氢原子.放电反应条件通过影响氢分子解离来影响氢气的催化作用.氢气在非平衡等离子体中显示的催化作用有可能为开辟新的化学合成途径提供重要机遇.     

聚苯胺盐在无溶剂条件下有效催化羰基保护反应

合成了自掺杂聚苯胺盐PABSA,并成功应用于醛和乙酸酐的缩醛化反应,发现此聚苯胺盐催化剂具有高效、可回收等特性。同时,利用二元醇作为保护基团,醛也可以转化成相应的缩醛。考察了反应时间、温度和催化剂用量对反应的影响,并通过IR、1H NMR、13C NMR和元素分析对部分产物进行了结构表征。