Mahmoud Zendehdel

Electrochemical reduction of carbon dioxide to methanol represents one of the most demanding transformations in CO ₂ conversion, requiring the management of a six-electron, six-proton sequence while suppressing competing pathways toward carbon monoxide, formate, and hydrogen evolution. Among molecular electrocatalysts, cobalt phthalocyanine (CoPc) has emerged as a unique molecular platform capable of extending CO ₂ reduction beyond CO through a domino-like cascade of protoncoupled electron transfer steps. Its square-planar Co-N ₄ coordination environment provides metalcentered redox couples that enables CO ₂ activation at the Co(I) state and stabilizes key intermediates within a narrow adsorption-energy window compatible with further hydrogenation. This review examines the fundamental and applied aspects of CoPc-mediated electrochemical CO ₂ and CO reduction to methanol. The effects of ring substitution, axial ligation, and support-induced distortions on redox potentials, orbital interactions, and intermediate binding energetics were analyzed. Particular attention was devoted to solvation-coupled proton-coupled electron transfer, cation effects, and electric double-layer structure, which collectively governed CO retention and sequential hydrogenation toward CH ₃ OH. Immobilization strategies on carbon nanotubes and related supports were discussed in relation to molecular dispersion, electronic coupling, and stability under flow-cell operation. Finally, scalability and sustainability are assessed through life-cycle considerations and green-chemistry metrics applied to phthalocyanine synthesis and device integration. Despite these advances, the field remains limited by catalyst deactivation, incomplete comparability among electrochemical setups and the frequent lack of standardized metrics for methanol quantification under device-relevant conditions. By connecting molecular design interfacial microenvironment, reactor architecture and sustainable catalyst synthesis, this review identifies the key directions required to move CoPc-based systems from promising molecular models toward technologically credible CO ₂ -to-methanol electrolysis.

Hole transport layer (HTL) plays a vital role in perovskite solar cells (PSCs) and is one of the bottlenecks to further enhancements in device performance and stability. Currently the dominant choice as the hole transport material (HTM), 2,2′,7,7′‐tetrakis(N,N‐di‐p‐methoxyphenylamine)‐9,9′‐spirobifluorene (spiro‐OMeTAD), for n‐i‐p PSCs suffer from thermal and moisture instability and high fabrication cost. In this study, we investigated three potential HTMs to replace spiro‐OMeTAD—two polymeric materials, PTAA (poly[bis(4‐phenyl)(2,4,6‐trimethylphenyl)amine]) and P3HT (poly(3‐hexylthiophene‐2,5‐diyl)), and a molecular material, H101 (2,5‐bis(4,4′‐bis(methoxyphenyl)aminophen‐4″‐yl)‐3,4‐ethylenedioxythiophene). Among the candidates, PTAA‐based PSCs achieved the highest efficiency of 21.01%, outperforming spiro‐OMeTAD (18.95%), P3HT (17.81%), and H101 (16.93%). Detailed charge carrier dynamics analysis revealed that PTAA's superior performance is driven by its ability to suppress non‐radiative recombination at the perovskite/HTM interface, despite a slower charge transfer process compared to other HTMs. These findings suggest that PTAA, along with P3HT and H101, provides not only comparable but potentially superior device performance while offering opportunities to enhance device stability, highlighting the potential of alternative HTMs in advancing n‐i‐p PSC technologies.

We report a sustainable and cost‐effective synthesis of cobalt phthalocyanine (CoPc) using low‐impact solvents and a streamlined purification procedure, achieving an 85% yield with limited waste generation, as indicated by an environmental factor (E‐factor) of 18.6. This route provides an eco‐friendly approach to producing a molecular electrocatalyst for reduction. The catalytic activity of the synthesized CoPc is validated by its integration into a gas diffusion electrode with carbon nanotube supports, exhibiting methanol production with a Faradaic efficiency up to 12%, matching the values reached with the conventionally synthesized counterparts. Notably, under high loading (micrometric crystallites of CoPc), ‐to‐CO conversion reached 65%, in fair alignment with literature benchmarks. Our work shows that green synthesis can yield high‐performance catalysts for electrochemical reduction (), enabling sustainable methanol production.

Cost management and toxic waste generation are two key issues that must be addressed before the commercialization of perovskite optoelectronic devices. We report a groundbreaking strategy for eco-friendly and cost-effective fabrication of highly efficient perovskite solar cells. This strategy involves the usage of a high volatility co-solvent, which dilutes perovskite precursors to a lower concentration (1.4 M) solution. More than 70% of toxic waste and material cost can be reduced. Mechanistic insights reveal ultra-rapid evaporation of the co-solvent together with beneficial alteration of the precursor colloidal chemistry upon dilution with co-solvent, which in-situ studies and theoretical simulations confirm. The co-solvent tuned precursor colloidal properties also contribute to the enhancement of the stability of precursor solution, which extends its processing window thus minimizing the waste. This strategy is universally successful across different perovskite compositions, and scales from small devices to large-scale modules using industrial spin-coating, potentially easing the lab-to-fab translation of perovskite technologies.

Perovskite solar cells (PSCs) are a type of emerging thin‐film photovoltaics, which show a promising potential to catch a major portion of the near future market. However, hazardous waste‐generation and cost‐management of the industrial production are two key issues which need to be addressed in the commercialization process. Herein, a universal coating strategy is introduced by combination of blade and spin coating to realize a zero‐waste‐generation of the perovskite precursor materials for layer‐by‐layer deposition of 3D/2D perovskite films on large‐area substrates with high uniformity and reproducibility. This leads to eliminate 90% and 95% of the materials consumption compared to the conventional spin‐coating for deposition of the 3D and 2D perovskite layers, respectively, without changing of the ink precursor. Large‐area PSCs have been realized by blade–spin/blade coating approach reaching 19.55% photo‐conversion efficiency (PCE) over 0.92 cm² masked area and >1000 h T90 thermal stability at 85 °C. Fabricated perovskite solar modules via blade–spin/blade deposition have been reached to 18.8% PCE over 10 cm² active‐area. The economic analysis shows the potential for >90% decrease of the operational expenditure via break‐down of the material costs from 1.99 € m⁻² in spin coating method to 0.18 € m⁻² in blade–spin/blade coating approach.

Polyacrylonitrile (PAN) fibers with unique properties are becoming increasingly important as precursors for the fabrication of carbon fibers. Here, we suggest the preparation of porous PAN composite fibers to increase the homogeneity and thermal stability of the fibers. Based on the thermodynamics of polymer solutions, the ternary phase diagram of the PAN/H₂O/Dimethylformamide (DMF) system has been modeled to introduce porosity in the fibers. Adding a conscious amount of water (4.1 wt.%) as a non-solvent to the PAN solution containing 1 wt.% of graphene oxide (GO), followed by wet spinning, has led to the preparation of porous composite fibers with high thermal stability and unique physicochemical properties. Differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) results elucidate that PAN/GO/H₂O porous composite fibers have a higher thermal decomposition temperature, increased residual weight, reduced heat release rate, and higher crystallinity in comparison with the pristine PAN fibers, being a promising precursor for the development of high-performance carbon fibers. The results show a promising application window of the synthesized PAN fibers in electronic and electrochemical devices.

Utilizing of photovoltaics (PVs) has been rapidly developing over the past two decades due to its potential for transition from fossil fuels to renewable energy based economies. However, PVs as fuel less energy sources will be sustainable if some issues such as raw materials abundance, production cost, and environmental impacts carefully addressed in their value chains. Among PV technologies, thin film solar panels have been illustrated the potential to reach the sustainability. In this chapter we review some studies about environmental impacts of thin film PVs through life cycle assessment (LCA) and some environmental fate modeling. For the PV technologies, LCA studies need to be conducted to address environmental and energy impacts and encourage the development of PV technologies in a better sustainable way. Three methods of impact assessment in LCA are reviewed and compared, namely, Energy Payback Time (EPBT), Cumulative Energy Demand (CED), and Greenhouse Gases (GHG) emission rate, owing to data and information published in the literature. Generally, most results show promising potential of emerging thin film PVs, especially perovskite solar cells, to reach the best sustainable solution among PV technologies in near future.