In recent years, there has been significant interest in photocatalytic technologies utilizing semiconductors and photosensitizers responsive to solar light, owing to their potential for energy and environmental applications. Current efforts are focused on enhancing existing photocatalysts and developing new ones tailored for environmental uses. Anthraquinones (AQs) serve as redox-active electron transfer mediators and photochemically active organic photosensitizers, effectively addressing common issues such as low light utilization and carrier separation efficiency found in conventional semiconductors. AQs offer advantages such as abundant raw materials, controlled preparation, excellent electron transfer capabilities, and photosensitivity, with applications spanning the energy, medical, and environmental sectors. Despite their utility, comprehensive reviews on AQs-based photocatalytic systems in environmental contexts are lacking. In this review, we thoroughly describe the photochemical properties of AQs and their potential applications in photocatalysis, particularly in addressing key environmental challenges like clean energy production, antibacterial action, and pollutant degradation. However, AQs face limitations in practical photocatalytic applications due to their low electrical conductivity and solubility-related secondary contamination. To mitigate these issues, the design and synthesis of graphene-immobilized AQs are highlighted as a solution to enhance practical photocatalytic applications. Additionally, future research directions are proposed to deepen the understanding of AQs\' theoretical mechanisms and to provide practical applications for wastewater treatment. This review aims to facilitate mechanistic studies and practical applications of AQs-based photocatalytic technologies and to improve understanding of these technologies.

Methanogens are the main participants in the carbon cycle, catalyzing five methanogenic pathways. Methanogens utilize different iron-containing functional enzymes in different methanogenic processes. Iron is a vital element in methanogens, which can serve as a carrier or reactant in electron transfer. Therefore, iron plays an important role in the growth and metabolism of methanogens. In this paper, we cast light on the types and functions of iron-containing functional enzymes involved in different methanogenic pathways, and the roles iron play in energy/substance metabolism of methanogenesis. Furthermore, this review provides certain guiding significance for lowering CH4 emissions, boosting the carbon sink capacity of ecosystems and promoting green and low-carbon development in the future.

The growing interest in green ammonia production has spurred the development of new catalysts with the potential to carry out the Haber-Bosch process under mild pressure and temperature conditions. While there is a wide experimental background on new catalysts involving transition metals, supports and additives, the fundamentals behind ammonia synthesis performance on these catalysts remained partially unsolved. Here, we review the most important works developed to date and analyze the traditional catalysts for ammonia synthesis, as well as the influence of the electron transfer properties of the so-called 3rd-generation catalysts. Finally, the importance of metal-support interactions is highlighted as an effective pathway for the design of new materials with potential to carry out ammonia synthesis at low temperatures and pressures.

Ammonium oxidation coupled to Fe(III) reduction (Feammox) is a newly discovered iron-nitrogen cycle process of microbial catalyzed NH4+ oxidation coupled with iron reduction. Fe(III) often exists in the form of insoluble iron minerals resulting in reduced microbial availability and low efficiency of Feammox. Electron shuttles(ESs) can be reversibly oxidized and reduced which has the potential to improve Feammox efficiency. This review summarizes the discovery process, electron transfer mechanism, influencing factors and driven microorganisms of Feammox, ang expounds the possibility and potential mechanism of ESs to enhance Feammox efficiency. Based on an in-depth analysis of the current research situation of Feammox for nitrogen removal, the knowledge gaps and future research directions including how to apply ESs enhanced Feammox to promote nitrogen removal in practical wastewater treatment have been highlighted. This review can provide new ideas for the engineering application research of Feammox and strong theoretical support for its development.

Polybrominated diphenyl ethers (PBDEs) are widely used as brominated flame retardants, which had attracted amounts of attention due to their harmful characteristics of high toxicity, environmental persistence and potential bioaccumulation. Many chemical reductive debromination technologies have been developed for the debromination of PBDEs, including photolysis, photocatalysis, electrocatalysis, zero-valent metal reduction, chemically catalytic reduction and mechanochemical method. This review aims to provide information about the degradation thermodynamics and kinetics of PBDEs and summarize the degradation mechanisms in various systems. According to the comparative analysis, the rapid debromination to generate bromine-free products in an electron-transfer process, of which photocatalysis is a representative one, is found to be relatively difficult, because the degradation rate of PBDEs depended on the Br-rich phenyl ring with the lowest unoccupied molecular orbital (LUMO) localization. On the contrary, the complete debromination occurs easily in other systems with active hydrogen atoms as the main reactive species, such as chemically catalytic reduction systems. The review provides the knowledge on the chemical reductive technique of PBDEs, which would greatly help not only clarify the degradation mechanism but also design the more efficient system for the rapid and deep debromination of PBDEs in the future.

A majority of clay minerals contain Fe, and the redox cycling of Fe(III)/Fe(II) in clay minerals has been extensively studied as it may fuel the biogeochemical cycles of nutrients and govern the mobility, toxicity and bioavailability of a number of environmental contaminants. There are three types of Fe in clay minerals, including structural Fe sandwiched in the lattice of clays, Fe species in interlayer space and adsorbed on the external surface of clays. They exhibit distinct reactivity towards contaminants due to their differences in redox properties and accessibility to contaminant species. In natural environments, microbially driven Fe(III)/Fe(II) redox cycling in clay minerals is thought to be important, whereas reductants (e.g., dithionite and Fe(II)) or oxidants (e.g., peroxygens) are capable of enhancing the rates and extents of redox dynamics in engineered systems. Fe(III)-containing clay minerals can directly react with oxidizable pollutants (e.g., phenols and polycyclic aromatic hydrocarbons (PAHs)), whereas structural Fe(II) is able to react with reducible pollutants, such as nitrate, nitroaromatic compounds, chlorinated aliphatic compounds. Also structural Fe(II) can transfer electrons to oxygen (O2), peroxymonosulfate (PMS), or hydrogen peroxide (H2O2), yielding reactive radicals that can promote the oxidative transformation of contaminants. This review summarizes the recent discoveries on redox reactivity of Fe in clay minerals and its links to fates of environmental contaminants. The biological and chemical reduction mechanisms of Fe(III)-clay minerals, as well as the interaction mechanism between Fe(III) or Fe(II)-containing clay minerals and contaminants are elaborated. Some knowledge gaps are identified for better understanding and modelling of clay-associated contaminant behavior and effective design of remediation solutions.

The removal of environmental pollutants is important for a sustainable ecosystem and human health. Shewanella oneidensis (S. oneidensis) has diverse electron transfer pathways and can use a variety of contaminants as electron acceptors or electron donors. This paper reviews S. oneidensis\'s function in removing environmental pollutants, including heavy metals, inorganic non-metallic ions (INMIs), and toxic organic pollutants. S. oneidensis can mineralize o-xylene (OX), phenanthrene (PHE), and pyridine (Py) as electron donors, and also reduce azo dyes, nitro aromatic compounds (NACs), heavy metals, and iodate by extracellular electron transfer (EET). For azo dyes, NACs, Cr(VI), nitrite, nitrate, thiosulfate, and sulfite that can cross the membrane, S. oneidensis transfers electrons to intracellular reductases to catalyze their reduction. However, most organic pollutants cannot be directly degraded by S. oneidensis, but S. oneidensis can remove these pollutants by self-synthesizing catalysts or photocatalysts, constructing bio-photocatalytic systems, driving Fenton reactions, forming microbial consortia, and genetic engineering. However, the industrial-scale application of S. oneidensis is insufficient. Future research on the metabolism of S. oneidensis and interfacial reactions with other materials needs to be deepened, and large-scale reactors should be developed that can be used for practical engineering applications.

Electrochemical impedance spectroscopy (EIS) is an efficient and non-destructive test for analyzing the bioelectrochemical processes of microbial fuel cells (MFCs). The key factors limiting the output performance of an MFC can be identified by quantifying the contribution of its various internal parts to the total impedance. However, little attention has been paid to the measurement conditions and diagrammatic processes of the EIS for MFC. This review, starting with the analysis of admittance of bioelectrode, introduces conditions for the EIS measurement and summarizes the representative equivalent circuit plots for MFC. Despite the impedance from electron transfer and diffusion process, the effect of unnoticeable capacitance obtained from the Nyquist plot on MFCs performance is evaluated. Furthermore, given that distribution of relaxation times (DRT) is an emerging method for deconvoluting EIS data in the field of fuel cell, the application of DRT-analysis to MFC is reviewed here to get insight into bioelectrode reactions and monitor the biofilm formation. Generally, EIS measurement is expected to optimize the construction and compositions of MFCs to overcome the low power generation.

Given the rapid development of technologies in biochemical engineering and genetic engineering, biological capture, conversion and utilization of greenhouse gases (carbon dioxide and methane) into value-added products have been progressed rapidly. The efficiency of electron transfer and energy supply are essential for microbial carbon fixation. In this review, the concepts of direct and indirect electron transfer chains in methanotrophic and chemoautotrophic microbes were introduced firstly. Subsequently, the strategies of supplying light and electrical energy as well as their effects on metabolic flux, synthetic pathway and energy supply efficiency during microbial carbon fixation were discussed. Finally, solutions and application prospects to address the key technical challenges of microbial carbon fixation were discussed.

Photocatalysis is a green approach frequently utilised to eliminate a variety of environmentally hazardous refractory pollutants. Accordingly, the modification of semiconductor photocatalysts with Carbon Quantum Dots (CQDs) is of great importance for the treatment of such pollutants due to their attractive physical and chemical properties. CQDs are a perfect candidate to handle photocatalysts of high-performance since they operate as co-catalysts and as visible light harvesters. The higher separation rate of electron-hole pairs in the photocatalytic system is attributable to better photodegradation efficiency. This review classifies CQD based photocatalysts as pure, doped and composite materials and discusses the specific advantages of CQDs in visible light-driven photocatalysis. In this work, the versatile roles of CQDs in CQD-based photocatalytic systems are thoroughly discussed and summarised.