Natural mineral photoelectric effect: mineral non-classical photosynthesis

Under the ever-present solar radiation, photosynthetic organisms on Earth evolved structurally-sophisticated photosynthetic systems. However, little attention has been paid to the inherent impact of sunlight illumination on the inorganic minerals widespread on the Earth surface. We discovered for the first time the solar energy conversion system of the “mineral coatings” on the Earth's surface (aka“mineral membrane”), which exerts potential oxygen-production and carbon-sequestration functions on the Earth surface. Our finding shed a light on the photoelectric effect and non-classical photosynthesis involving natural semiconducting minerals. In this contribution, we studied the semiconducting property and photoelectron energy of typical minerals in the “mineral membrane”, focusing primarily on the photoelectric effect in and oxygen-production/carbon-sequestration function of ferromanganese oxides, as well as relevant geological records. We propose that birnessite, goethite and hematite, the semiconducting minerals commonly found in the “mineral membrane”, can perform sensitive and stable photon-to-electron conversion under solar radiation. The non-classical mineral photosynthetic function we put forth is as follows: Solar energy utilization by inorganic minerals resembles photosynthesis in regarding to oxygen evolution and carbon fixing, and the “mineral membrane” may take part in both photocatalytic water-oxidation reaction and transformation of atmospheric CO₂into marine carbonate. In addition, minerals might as well have promoted photosynthesis in photosynthetic organisms. During the water-oxidation reaction, the inorganic cluster Mn₄CaO₅of photosystem II cycles through redox intermediates that are analogous to birnessite both in structure and component. Thus, it is fair to postulate that birnessites could play a role in the initiation of the photosynthesis in cyanobacteria, as minerals could weaken the hydrogen bond strength and alter water properties, thus facilitating water oxidation and photosynthesis. This observation offers further insights into the molecular mechanism of mineral participation in photosynthesis in photosynthetic organisms.     

光电子作用下土壤微生物粪产碱杆菌反硝化性能研究

本文在对普通培养条件下异养微生物粪产碱杆菌(Alcaligenes faecalis,A.faecalis)反硝化特征研究的基础上,运用电化学方法于一定电势下(-0.15 V、-0.06 V、+0.06 V vs.NHE)模拟半导体矿物导带光电子能量,探讨不同能量的光电子对A.faecalis反硝化特性及细胞生长代谢的影响。实验显示,在普通培养条件下,A.faecalis在有氧和无氧环境中均不能还原NO-3,但还原NO-2效果明显。在模拟光电子实验体系中,A.faecalis可在不同电势(-0.15 V、-0.06 V、+0.06 V)的阴极石墨电极表面附着并形成具有反硝化活性的菌膜;其中,外加电势为-0.15V的实验组菌膜量最多,其NO-3去除率也最高,10天达到52%;-0.06 V体系略低,NO-3去除率为30.5%,+0.06 V体系菌膜量最少,其NO-3去除效果也最差,仅为10.6%。而在不添加微生物的电化学体系中,3个外加电势下的NO-3浓度均未发生明显变化。本实验研究结果证明了一定能量的半导体矿物光电子可影响土壤异养微生物A.faecalis的生长代谢及反硝化行为。     

铀矿物和含铀矿石中铀价态比值的X射线光电子能谱分析

在应用Ｘ射线光电子能谱对铀氧化物中铀价态比值定量分析的基础上，研究了对铀矿物和含铀矿石中铀价态的测量方法。结果表明，从含铀量０．９％－７２％的样品测得的Ｕ４＋／Ｕ总的比值与化学方法的结果相符。其分析误差能满足铀矿地质研究的需要。     

Crystal orbital contributions to the pyrrhotite valence band with XPS evidence for weak Fe–Fe π bond formation

 Synchrotron excited X-ray photoelectron spectra (SXPS) of hexagonal pyrrhotite reveal three distinct Fe 3d-derived photopeaks within its outer valence band. The t _2gα band (majority spin) is centered at about 2.5 eV, the e _g α band at about 1.0 eV and the t _2gβ (minority spin) contribution at about 0.25 eV. From these data the ligand field splitting energy is 1.5 (±0.2) eV and the majority spin pairing energy is 2.25 (±0.2) eV. These are the first such XPS measurements for this mineral. S 3p-derived bonding and non-bonding bands are identified, with the former centred at about 6.5 eV and the latter near 4.5 eV. The XPS results are remarkably consistent with SCF-Xα scattered wave molecular orbital calculations. Although the calculations and the collected spectra are consistent, they differ from a recent interpretation of the pyrrhotite valence band. An explanation for the discrepant results is provided. Auger resonant enhancement of Fe 3d photopeaks at 60 eV photon energy results in the t _2gα emission (at 2.5 eV) being strongly enhanced and broader than the t _2gβ emission (0.25 eV). The explanation of these observations requires the presence of weak Fe–Fe π and π^* crystal (molecular) orbitals located near 2.5 eV, and separated by no more than about 0.5 eV. The π-bonded crystal orbitals are derived from weak mixing of adjacent Fe t _2g atomic orbitals along the c crystallographic axis. Received: 15 June 2000 / Accepted: 11 June 2001     

X射线光电光谱表征金属氧化物的酸碱性

本文探讨了氧配位的八面体及四面体的金属配合物中氧原子的价态变化及其酸碱性差异之间的关系。首先利用X射线光电光谱（XPS）分别推导出了氧原子在碱及碱土铝酸盐、铬酸盐、高铁酸盐、钼酸盐及钨酸盐中的价态,随后对氧原子的价态及氧化物的酸碱性质进行了比较。研究结果表明,氧原子的价态在这两种配位构型的化合物中没有显著的差别,其酸碱性的不同在于四面体配位的金属化合物中O2p态在非成键和成键的电子密度中高价带的分裂。     

地表“矿物膜”半导体矿物光电子调控微生物群落结构演化特性研究

矿物-微生物交互作用广泛参与地球表层系统物质循环与能量流动过程,深刻地影响着一系列重要的地表生物地球化学进程。近年来地表半导体矿物的相关研究,为矿物-微生物交互作用提供了崭新研究方向,揭示地表“日光-半导体矿物-微生物”系统电子传递过程及其环境效应,是地质微生物学交叉领域研究的核心科学问题之一。本研究从地表不同生境“矿物膜”出发,以光电化学技术证实喀斯特、红壤、岩石漆“矿物膜”在1 000 min长时间循环实验中平均光电流值约为5.4、3.4、3.2 μA/cm²,证实“矿物膜”良好日光响应特性且铁锰氧化物矿物在其中发挥核心作用。基于笔者前期研究所发现的“矿物膜”电活性菌富集且与半导体矿物分布呈正相关性这一现象,本文进一步构建模拟光电子红壤细菌群落系统,20天后细菌群落α多样性显著提升,研究证实细菌群落具有模拟光电子响应活性,且电极与溶液群落均具有演化方向性;16S rRNA测序分析表明模拟光电子作用下Shewanella、Pseudomonas、Streptococcus、Lactobacillus、Acinetobacter等电活性菌显著富集。综上,本文研究结果间接证实地表半导体矿物光电子可有效调控微生物群落结构并促进电活性菌在“矿物膜”中富集。     

X-ray photoelectron study of oxygen bonding in crystalline C–S–H phases

We recorded the photoelectron spectra of various crystalline calcium silicate hydrates (C–S–Hs) and have examined their O 1 s photoelectron spectra. The spectra are asymmetric, with contributions assigned primarily to bridging and non-bridging oxygen species. There is an increased contribution due to the presence of non-bonding oxygen atoms with increasing calcium:silicon ratio. Additionally, there are slight changes in theO 1s-binding energies with changes in calcium:silicon ratio. These changes are explained in terms of bonding and silicate structure.     

黄铁矿及毒砂中负氧化数金的发现及判定

作者在以突破金的氧化态（价态）为先导的研究中，使用光电子能谱对９个金矿区的黄铁矿与毒砂进行了研究。发现它们之中广泛出现有结合能为８３（８２．８～８３．２）ｅＶ的峰，经分析对比后，指认它为Ａｕ峰（４ｆ＿（７／２）。但它的结合能小于Ａｕ￣０（约８４ｅＶ），更小于Ａｕ￣（１＋）及Ａｕ￣（３＋）．根据结合能与氧化态的关系，判定８３ｅＶ峰为负氧化数金（负价金）所引起。即黄铁矿与毒砂中存在有负氧化数金。     

地表“矿物膜”:地球“新圈层”

地球表层是一个极为复杂的开放系统,其中所充满的阳光、大气、水分、有机酸、无机酸/盐、矿物质和微生物等彼此之间无时无刻不在发生着人们尚未充分认识到的多种自然作用。本文采用环境矿物学、半导体物理学与光电化学等交叉学科研究手段,在我国南方红壤、西南喀斯特和西北戈壁等典型陆地生境中,发现直接暴露于太阳光下的土壤/岩石表面广泛发育有几十纳米到数百微米厚度的铁锰氧化物"矿物膜";详细研究了铁锰氧化物"矿物膜"中矿物组成及其精细结构特征,发现半导体性能优异的水钠锰矿普遍存在,其晶体结构中富含促进其光催化功能的稀土元素Ce。在这些生境中,矿物岩石表面所包覆的铁锰氧化物"矿物膜"总是朝着太阳光发育,岩石背面却不出现"矿物膜",揭示出太阳光照射下的地球陆地表面普遍存在的"矿物膜"与太阳光有着直接的响应关系。光电化学测试结果显示,天然"矿物膜"具有较好的日光响应性能,由其制成的电极在可见光照射下皆能产生明显的光电流,而不含铁锰氧化物矿物的岩石基质样品及石英、长石等矿物样品几乎不产生光电流,表明"矿物膜"光电流的产生主要与铁锰氧化物有关。进一步测得"矿物膜"中主要铁锰氧化物的禁带宽度均小于2. 5eV,证明其均为对可见光具有广泛而良好吸收的天然半导体矿物。以全球日光平均辐照强度100mW/cm~2计以及全球典型生境中"矿物膜"分布面积估算,全球"矿物膜"吸收太阳能等效为生物质能的最大量与2017年度全球糖类产量(1. 92亿吨)相当。铁锰氧化物"矿物膜"不仅存在于陆地地表,还存在于海洋透光层中。可以认为地表"矿物膜"是地球上分布最广的天然"太阳能薄膜",从功能上"矿物膜"相当于继地核、地幔和地壳之后的地球第四大圈层,事实上构成了地球"新圈层",也是地球在太阳光能量驱动下发生外营力地质作用的关键地带。在此基础上,本文提出从"矿物膜"中产生的矿物光电子与太阳光子和元素价电子共同组成了地表存在的三种主要能量形式的认识。深入探讨太阳光照射下地表多圈层交互作用界面上所发生的电子传递与能量转化的微观机制,有助于深刻理解地表"矿物膜"这一地球"新圈层"如何影响地球物质演化、生命起源进化与环境变化演变的宏观过程。     

矿物光电子能量在地球早期生命起源与进化中的作用

地球早期生命起源的第一步是合成简单的有机化合物,但合成有机物所需能量来源问题长期困扰着学术界。早期地球上丰富的硫化物半导体矿物可将太阳光子转化为光电子,提供持续的能量来源。也正是由于矿物光电子能量较高,在非生物途径合成小分子有机物方面具有优势。其中半导体矿物自然硫转化太阳能产生的光电子能量,是目前所发现的最高的矿物光电子能量,不仅能直接还原CO₂分子为甲酸物质,还可催化其他生命基础物质的合成。在全球陆地系统中暴露在阳光下的岩石/土壤表面普遍被一层铁锰氧化物“矿物膜”所覆盖,光照下含半导体矿物水钠锰矿的“矿物膜”产生原位、灵敏、长效的光电流,显示出优异的光电效应。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结构中间体,地球早期“矿物膜”中水钠锰矿可能促进了锰簇Mn₄CaO₅与生物光合作用的起源与进化。早期地球半导体矿物为生命起源基本物质的合成提供直接能量来源,矿物光电子能量在地球早期生命起源与进化中起到了重要作用。