Fabricating Dual-Atom Iron Catalysts for Efficient Oxygen Evolution Reaction: A Heteroatom Modulator Approach

Understanding the thermal aggregation behavior of metal atoms is important for the synthesis of supported metal clusters. Here, derived from a metal–organic framework encapsulating a trinuclear Fe^III₂Fe^II complex (denoted as Fe₃) within the channels, a well-defined nitrogen-doped carbon layer is fabricated as an ideal support for stabilizing the generated iron nanoclusters. Atomic replacement of Fe^II by other metal(II) ions (e.g., Zn^II/Co^II) via synthesizing isostructural trinuclear-complex precursors (Fe₂Zn/Fe₂Co), namely the “heteroatom modulator approach”, is inhibiting the aggregation of Fe atoms toward nanoclusters with formation of a stable iron dimer in an optimal metal–nitrogen moiety, clearly identified by direct transmission electron microscopy and X-ray absorption fine structure analysis. The supported iron dimer, serving as cooperative metal–metal site, acts as efficient oxygen evolution catalyst. Our findings offer an atomic insight to guide the future design of ultrasmall metal clusters bearing outstanding catalytic capabilities.     

Strategies for Improving the Catalytic Performance of 2D Covalent Organic Frameworks for Hydrogen Evolution and Oxygen Evolution Reactions

Hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) have been deemed as clean and sustainable strategies to solve the energy crisis and environmental problems. Various catalysts have been developed to promote the process of HER and OER. Among them, two-dimensional covalent organic frameworks (2D COFs) have received great attention due to their diverse and designable structure. In this minireview, we mainly summarize the diverse linkages of 2D COFs and strategies for enhancing the catalytic performance of 2D COFs for HER and OER, such as introducing active building blocks, metal ions and tailored linkages. Furthermore, a brief outlook for the development directions of COFs in the field of HER and OER is provided, expecting to stimulate new opportunities in future research.     

Time dependent Schrödinger equation for black hole evaporation: No information loss

In 1976 S. Hawking claimed that “Because part of the information about the state of the system is lost down the hole, the final situation is represented by a density matrix rather than a pure quantum state”. ¹ This was the starting point of the popular “black hole (BH) information paradox”.     

紫色球杆菌视紫红质光谱特性的机器学习研究

近年来，机器学习等人工智能技术被应用于蛋白质工程，其在蛋白质结构、功能预测、催化活性等研究中具有独特优势。在未知蛋白质结构的情况下，将蛋白质序列和功能特性与机器学习相结合，基于序列-活性关系（innovative sequence-activity relationship，ISAR）算法，将蛋白质氨基酸序列数字化，用快速傅里叶变换（fast four transform，FFT）进行预处理，再进行偏最小二乘回归建模，可在数据集较少情况下拟合得到最佳模型。通过机器学习对紫色球杆菌视紫红质（gloeobacter violaceus rhodopsin，GR）的突变体蛋白质氨基酸序列与光谱最大吸收波长进行建模，获得了最佳模型。用最佳索引LEVM760106建模得到的确定系数R² 为0.944，均方误差E为11.64。用小波变换进行的预处理，其R² 虽也约为0.944，但E大于11.64，不及FFT进行的预处理。方法较好地解决了蛋白质序列与功能特性之间的数学建模问题，在蛋白质工程中可为预测更优的突变体提供支持。     

A molecular fluorophore in citric acid/ethylenediamine carbon dots identified and quantified by multinuclear solid-state nuclear magnetic resonance

The composition of fluorescent polymer nanoparticles, commonly referred to as carbon dots, synthesized by microwave-assisted reaction of citric acid and ethylenediamine was investigated by ¹³C, ¹³C{¹H}, ¹H─¹³C, ¹³C{¹⁴N}, and ¹⁵N solid-state nuclear magnetic resonance (NMR) experiments. ¹³C NMR with spectral editing provided no evidence for significant condensed aromatic or diamondoid carbon phases. ¹⁵N NMR showed that the nanoparticle matrix has been polymerized by amide and some imide formation. Five small, resolved ¹³C NMR peaks, including an unusual ═CH signal at 84 ppm (¹H chemical shift of 5.8 ppm) and ═CN₂ at 155 ppm, and two distinctive ¹⁵N NMR resonances near 80 and 160 ppm proved the presence of 5-oxo-1,2,3,5-tetrahydroimidazo[1,2-a]pyridine-7-carboxylic acid (IPCA) or its derivatives. This molecular fluorophore with conjugated double bonds, formed by a double cyclization reaction of citric acid and ethylenediamine as first shown by Y. Song, B. Yang, and coworkers in 2015, accounts for the fluorescence of the carbon dots. Cross-peaks in a ¹H─¹³C HETCOR spectrum with brief ¹H spin diffusion proved that IPCA is finely dispersed in the polyamide matrix. From quantitative ¹³C and ¹⁵N NMR spectra, a high concentration (18 ± 2 wt%) of IPCA in the carbon dots was determined. A pronounced gradient in ¹³C chemical-shift perturbations and peak widths, with the broadest lines near the COO group of IPCA, indicated at least partial transformation of the carboxylic acid of IPCA by amide or ester formation.     

Spectral estimates for saddle point matrices arising in weak constraint four‐dimensional variational data assimilation

We consider the large sparse symmetric linear systems of equations that arise in the solution of weak constraint four‐dimensional variational data assimilation, a method of high interest for numerical weather prediction. These systems can be written as saddle point systems with a 3 × 3 block structure but block eliminations can be performed to reduce them to saddle point systems with a 2 × 2 block structure, or further to symmetric positive definite systems. In this article, we analyse how sensitive the spectra of these matrices are to the number of observations of the underlying dynamical system. We also obtain bounds on the eigenvalues of the matrices. Numerical experiments are used to confirm the theoretical analysis and bounds.     

Cobalt Based Nanoparticles Embedded Reduced Graphene Oxide Aerogel for Hydrogen Evolution Electrocatalyst

Efficient water electrolysis catalyst is highly demanded for the production of hydrogen as a sustainable energy fuel. It is reported that cobalt derived nanoparticle (CoS₂, CoP, CoS|P) decorated reduced graphene oxide (rGO) composite aerogel catalysts for highly active and reliable hydrogen evolution reaction electrocatalysts. 7 nm level cobalt derived nanoparticles are synthesized over graphene aerogel surfaces with excellent surface coverage and maximal expose of active sites. CoS|P/rGO hybrid aerogel composites show an excellent catalytic activity with overpotential of ≈169 mV at a current density of ≈10 mA cm^?2. Accordingly, efficient charge transfer is attained with Tafel slope of ≈52 mV dec^?1 and a charge transfer resistance (R_ct) of ≈12 Ω. This work suggests a viable route toward ultrasmall, uniform nanoparticles decorated graphene surfaces with well‐controlled chemical compositions, which can be generally useful for various applications commonly requiring large exposure of active surface area as well as robust interparticle charger transfer.     

Recent Progress on Nickel-Based Oxide/(Oxy)Hydroxide Electrocatalysts for the Oxygen Evolution Reaction

Developing clean and sustainable energies as alternatives to fossil fuels is in strong demand within modern society. The oxygen evolution reaction (OER) is the efficiency-limiting process in plenty of key renewable energy systems, such as electrochemical water splitting and rechargeable metal–air batteries. In this regard, ongoing efforts have been devoted to seeking high-performance electrocatalysts for enhanced energy conversion efficiency. Apart from traditional precious-metal-based catalysts, nickel-based compounds are the most promising earth-abundant OER catalysts, attracting ever-increasing interest due to high activity and stability. In this review, the recent progress on nickel-based oxide and (oxy)hydroxide composites for water oxidation catalysis in terms of materials design/synthesis and electrochemical performance is summarized. Some underlying mechanisms to profoundly understand the catalytic active sites are also highlighted. In addition, the future research trends and perspectives on the development of Ni-based OER electrocatalysts are discussed.