Theory of chemical bonds in metalloenzymes XXII: a concerted bond-switching mechanism for the oxygen–oxygen bond formation coupled with one electron transfer for water oxidation in the oxygen-evolving complex of photosystem II

ABSTRACT

QM(UB3LYP)/MM(AMBER) calculations were performed for the locations of the transition structure (TS) of the oxygen–oxygen (O–O) bond formation in the S₄ state of the oxygen-evolving complex (OEC) of photosystem II (PSII). The natural orbital (NO) analysis of the broken-symmetry (BS) solutions was also performed to elucidate the nature of the chemical bonds at TS on the basis of several chemical indices defined by the occupation numbers of NO. The computational results revealed a concerted bond switching (CBS) mechanism for the oxygen–oxygen bond formation coupled with the one-electron transfer (OET) for water oxidation in OEC of PSII. The orbital interaction between the σ-HOMO of the Mn(IV)₄–O₍₅₎ bond and the π*-LUMO of the Mn(V)₁=O₍₆₎ bond plays an important role for the concerted O–O bond formation for water oxidation in the CaMn₄O₆ cluster of OEC of PSII. One electron transfer (OET) from the π-HOMO of the Mn(V)₁=O₍₆₎ bond to the σ*-LUMO of the Mn(IV)₄–O₍₅₎ bond occurs for the formation of electron transfer diradical, where the generated anion radical [Mn(IV)₄–O₍₅₎]^-? part is relaxed to the ?Mn(III)₄?…?O₍₅₎^- structure and the cation radical [O₍₆₎=Mn(V)₁]⁺ ? part is relaxed to the ⁺O₍₆₎–Mn(IV)₁? structure because of the charge-spin separation for the electron-and hole-doped Mn–oxo bonds. Therefore, the local spins are responsible for the one-electron reductions of Mn(IV)₄->Mn(III)₄ and Mn(V)₁->Mn(IV)₁. On the other hand, the O₍₅₎^- and O₍₆₎⁺ sites generated undergo the O–O bond formation in the CaMn₄O₆ cluster. The Ca(II) ion in the cubane- skeleton of the CaMn₄O₆ cluster assists the above orbital interactions by the lowering of the orbital energy levels of π*-LUMO of Mn(V)₁=O₍₆₎ and σ*-LUMO of Mn(IV)₄–O₍₅₎, indicating an important role of its Lewis acidity. Present CBS mechanism for the O–O bond formation coupled with one electron reductions of the high-valent Mn ions is different from the conventional radical coupling (RC) and acid-base (AB) mechanisms for water oxidation in artificial and native photosynthesis systems. The proton-coupled electron transfer (PC-OET) mechanism for the O–O bond formation is also touched in relation to the CBS-OET mechanism.     

Enhancing the Water Stability of Al‐MIL‐101‐NH2 via Postsynthetic Modification

The resistance of metal–organic frameworks towards water is a very critical issue concerning their practical use. Recently, it was shown for microporous MOFs that the water stability could be increased by introducing hydrophobic pendant groups. Here, we demonstrate a remarkable stabilisation of the mesoporous MOF Al‐MIL‐101‐NH₂ by postsynthetic modification with phenyl isocyanate. In this process 86 % of the amino groups were converted into phenylurea units. As a consequence, the long‐term stability of Al‐MIL‐101‐URPh in liquid water could be extended beyond a week. In water saturated atmospheres Al‐MIL‐101‐URPh decomposed at least 12‐times slower than the unfunctionalised analogue. To study the underlying processes both materials were characterised by Ar, N₂ and H₂O sorption measurements, powder X‐ray diffraction, thermogravimetric and chemical analysis as well as solid‐state NMR and IR spectroscopy. Postsynthetic modification decreased the BET equivalent surface area from 3363 to 1555 m² g^?1 for Al‐MIL‐101‐URPh and reduced the mean diameters of the mesopores by 0.6 nm without degrading the structure significantly and reducing thermal stability. In spite of similar water uptake capacities, the relative humidity‐dependent uptake of Al‐MIL‐101‐URPh is slowed and occurs at higher relative humidity values. In combination with ¹H‐²⁷Al D ‐HMQC NMR spectroscopy experiments this favours a shielding mechanism of the Al clusters by the pendant phenyl groups and rules out pore blocking.     

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.     

三维打印器件后处理液研究

分析了不同的填充强化剂(后处理A液)、不同的后处理B液基料、后处理B液中水性环氧乳液的掺量及后处理液浸泡时间对石膏基打印器件耐水性、抗压强度、尺寸偏差、表面微观结构的影响.结果表明:经纳米硅超硬固化剂处理后的打印器件抗压强度大幅提高,纳米硅超硬固化剂最适宜作为后处理A液;水性聚氨酯乳液PU-202B最适宜作为后处理B液的基料;后处理B液中加入水性环氧乳液,处理后打印器件的抗压强度增加、吸水率降低,但水性环氧乳液含量增加到一定程度后会出现尺寸偏差;后处理A、B液最佳浸泡时间分别为130 s和35 s;先浸泡后处理A液、后浸泡后处理B液的打印器件具有抗压强度高、吸水率小、表面较光滑、不脱粉等优良性能.     

超临界水氧化处理有机物废料的新技术

和传统方法相比，超临界水氧化处理有机物废料有着极大的优势。介绍了处理废料的原理和工业应用的可能性。     

Pilot Study on Nanofiltration Combined with Ozonation and GAC for Advanced Drinking Water Treatment

IntroductionThe conventional process for surface water treatment,which consists of flocculation, sedimentation and filtrationcurrently, had been applied inproducingdrinkingwater formany years. Although this process can remove turbidityand bacteria in surface water effectively, only about from20% to 30% of natural organic matter ( NOM) can beeliminated. When the purified water is disinfected bychlorination, these NOMs may react with chlorine. As aresult some dis…     

山西省吕梁区灌溉用水定额的编制

文章以调查典型县现状年灌溉用水定额为基础 ,以当地灌溉水可利用量为控制条件 ,采用逐级平衡的办法 ,制定吕梁区主要作物的灌溉用水定额     

给水处理系统高效经济运行的生产性评价

研究给水处理系统的高效经济运行技术 ,是保证水厂高效、安全、经济供水的重要措施 .生产运行实践证明 ,采用高效经济方式运行的确可以节约可变费用 .尤其是在冬季低温低浊水的净化中 ,可变费用的节约程度最高可达 2 0 %以上     

洼里煤矿综合防治水技术研究

龙矿集团洼里煤矿在生产过程中，针对主要含水层的不同赋存条件，有的放矢采取不同的防治措施。取得了显著的技术效果，保证了矿井的安全生产，对同类型煤矿防治水工作具有借鉴作用。     

线性回归分析与能源需求预测

结合实例介绍了回归模型方法在能源预测中的应用，具体地讨论了最简单、最基本的直线回归模型结构及参数估计方法，对于其他一些曲线回归模型则可通过变量代换转化为直线回归模型。