天然矿物光电效应:矿物非经典光合作用

doi:10.13745/j.esf.sf.2020.5.35

摘要/Abstract

摘要：

地球上生物因受到太阳光辐射作用而进化出结构精致的光合作用系统。太阳光辐射对地球表面广泛分布的无机矿物的影响与响应机制长期未被重视与理解。我们新发现的地表“矿物膜”转化太阳能系统,具有潜在的产氧固碳作用,体现出自然界中固有的矿物光电效应与非经典光合作用。本文在总结自然界中矿物光电子能量特征,特别是地表“矿物膜”特征及其光电效应性能的基础上,重点探讨铁锰氧化物矿物表现出的光电效应、产氧固碳作用与地质记录。提出矿物享有光电效应特性,地表“矿物膜”富含水钠锰矿、针铁矿、赤铁矿等天然半导体矿物,在日光辐射下具有稳定而灵敏的光电转换性能,产生矿物光电子能量;提出矿物拥有非经典光合作用的性能,自然界无机矿物转化太阳能系统类似生物光合作用吸收转化太阳能的产氧固碳系统,地表“矿物膜”光催化裂解水产氧作用及其转化大气和海洋二氧化碳为碳酸盐矿物作用,孕育出“矿物光合作用”;提出矿物具有促进生物光合作用的功能,生物光合作用中心Mn₄CaO₅在裂解水产氧过程中产生成分和结构类似水钠锰矿的锰簇化合物结构体,初步认为水钠锰矿可能促使蓝细菌光合作用系统的起源,矿物影响与削弱水分子氢键以改变水的性质,可提高水的分解程度与光合作用效率,为进一步探索矿物促进生物光合作用机理提供科学技术突破的机遇。

关键词: 矿物光电效应, 矿物非经典光合作用, 水钠锰矿, 矿物光电子能量, 产氧固碳作用

Abstract:

Under the ever-existing solar irradiation, the organisms on Earth have evolved with a structurally sophisticated photosynthesis system. However, the inherent impact and response mechanism of solar illumination on the inorganic minerals widespread on the Earth surface has drawn little attention. We discovered for the first time the solar energy conversion system of the “mineral membrane”, which exerts potential oxygen production and carbon sequestration functions on the Earth surface. Our finding shed light on the photoelectric effect and non-classical photosynthesis of the natural semiconducting minerals. We carried out this research on the semiconducting property and photoelectron energy of the typical minerals in the “mineral membrane”. We further discussed the photoelectric effect, oxygen production and carbon sequestration functions of the ferromanganese oxides, as well as the corresponding geological records. We proposed that the sensitive and stable photon-to-electron conversion are performed by birnessite, goethite and hematite, which are semiconducting minerals commonly present in the natural “mineral membrane”. In addition, we put forward the non-classical mineral photosynthesis function as follows: the solar energy conversion system developed by inorganic minerals resembles the biological photosynthesis process regarding to oxygen evolving and carbon fixing; also, the “mineral membrane” may take part in the photocatalytic water-oxidation reaction and in the transformation of atmospheric CO₂ into marine carbonate. Last but not least, minerals might as well have promoted the biologic photosynthesis system as the core complex in the Mn₄CaO₅ photosynthesis system evolved during water-oxidation process to form the structural analog birnessite. Therefore, it is fair to postulate that birnessite could play a role in the initiation of the photosynthesis system of cyanobacteria. On the other hand, minerals could weaken hydrogen bond strength and alter water property, thus to facilitate water oxidation and photosynthesis efficiencies, which would hopefully give further insights into the molecular mechanism of mineral participation in the biologic photosynthesis process.

Key words: mineral photoelectric effect, mineral non-classical photosynthesis, birnessite, mineral photoelectron energy, oxygen production and carbon sequestration

中图分类号:

P574
P571

鲁安怀, 李艳, 丁竑瑞, 王长秋, 许晓明, 刘菲菲, 刘雨薇, 朱莹, 黎晏彰. 天然矿物光电效应:矿物非经典光合作用[J]. 地学前缘, 2020, 27(5): 179-194.

LU Anhuai, LI Yan, DING Hongrui, WANG Changqiu, XU Xiaoming, LIU Feifei, LIU Yuwei, ZHU Ying, LI Yanzhang. Natural mineral photoelectric effect: non-classical mineral photosynthesis[J]. Earth Science Frontiers, 2020, 27(5): 179-194.

图/表 9

图1 自然界中三种重要能量形式——太阳光子、矿物光电子和元素价电子[2]

Fig.1 Three significant energy carriers in nature: solar photons, mineralphotoelectrons and elemental valence electrons. Adapted from [2].

图2 地表“矿物膜”构成地球“新圈层”[6]

Fig.2 A schematic diagram of the natural photosynthesis process, noting the “new sphere” of the “mineral membrane” as the topmost layer of the Earth surface. Adapted from [6].

图3 “矿物膜”产生原位、灵敏、稳定光电流[3]

Fig.3 In-situ, sensitive and stable photocurrent produced by the “mineral membrane”. Adapted from [3].

图4 自然光合作用和人工光合作用中Mn4CaO5的结构和性能比较[28]

Fig.4 Structural and functional comparisons of Mn4CaO5 in the natural and artificial photosynthesis processes. Adapted from [28].

图5 OEC催化中心5种不同的状态示意图[28,30]

Fig.5 Five different phases of the catalytic oxygen-evolving-centers (OEC). Adapted from [28,30].

图6 生物光合作用PSII产氧过程中Mn4CaO5结构变化特征[39]

Fig.6 Structural transformation of Mn4CaO5 during biologic photosynthesis-II and oxygen-evolving process. Adapted from [39].

表1 水钠锰矿与生物光合作用PSII产氧过程比较[39]

Table 1 Comparison of oxygen production mechanisms of birnessite and biologic photosynthesis-II. Adapted from [39].

光反应部位	催化状态	产氧过程
生物PSⅡ	S₁-S₃	Mn(Ⅲ)逐步被氧化
水钠锰矿	S₁-S₄	Mn(Ⅲ)逐步被氧化
生物PSⅡ	S₄	形成O—O键
水钠锰矿	S₅	形成O—O键
生物PSⅡ	S₄-S₀-S₁	Mn(Ⅳ)被还原,H₂O被氧化,释放O₂
水钠锰矿	S₅-S₆-S₁	Mn(Ⅳ)被还原,H₂O被氧化,释放O₂

图7 锰簇[Mn4O4L6]+光催化产氧过程中形成水钠锰矿物相[33] a—锰簇[Mn4O4L6]+光催化产氧过程;b—产物EXAFS图谱鉴定比较。

Fig.7 Birnessite phases produced in the [Mn4O4L6]+ catalytic oxygen-evolving process: (a) [Mn4O4L6]+ catalytic oxygen-evolving process; (b) Manganese K-edge EXAFS spectra of products. Adapted form [33].

图8 土壤中水钠锰矿转化二氧化碳为碳酸盐矿物的机制[54]

Fig.8 Transformation mechanism of CO2 to carbonate minerals by birnessite in soil. Adapted from [54].

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