Materials For Energy Conversion Research Articles

Advanced Magnetocaloric Materials for Energy Conversion: Recent Progress, Opportunities, and Perspective

AbstractSolid‐state caloric effects as intrinsic thermal responses to different physical external stimuli (magnetic‐, uniaxial stress‐, pressure‐, and electric‐fields) can achieve a higher energy efficiency compared with traditional gas compression techniques. Among these effects, magnetocaloric energy conversion is regarded as the best available alternative and has been exploited extensively for promising application scenarios in the last decades. This review systematically introduces the magnetocaloric effect and its applications, and summarizes the corresponding representative magnetocaloric materials, as well as important progress in recent years. Specifically, the review focuses on some key understandings of the magnetocaloric effect by utilizing state‐of‐the‐art technical tools such as synchrotron X‐ray, neutron scattering, muon spin spectroscopy, positron annihilation spectroscopy, high magnetic fields, etc., and highlights their importance toward advanced materials design and development. An overview of the basic principles and applications of these advanced techniques on magnetocaloric materials is provided. Finally, the challenges and perspectives on further developments in this field are discussed. Further in‐depth understanding and manufacturing technology advancement combined with fast‐developed artificial intelligence and machine learning are expected to advance the magnetocaloric energy conversion technology closer to real applications.

Biomass waste lotus shell-based shape-stabilized phase change composites with improved thermal conductivity for thermal management

Lotus shells represent an underutilized renewable resource with desirable porous architecture for producing bio-based phase change composites (PCMs). This research endeavors to fabricate a series of shape-stable phase change composites (SSPCCs) based on n-docosane (ND) and waste lotus shells to enhance heat utilization, solar photothermal energy conversion, and promote environmental protection. Both carbonization and activation processes play a critical role in the formation of desired pore structures. The carbonized lotus shells (CLS) and activated lotus shells (ALS) exhibit superior specific surface areas, reaching 147.70 m2/g for CLS and 1652.35 m2/g for ALS. Notably, the composite of ND integrated with ALS (ND/ALS) exhibits satisfactory latent heat storage of 93.68 J/g, excellent leakage prevention, and exceptional thermal cycle stability. Subsequently, the ND/ALS displays a significantly enhanced thermal conductivity of 0.482 W/(m·K) with an appreciable increment of 189% compared to ND. Furthermore, the obtained SSPCCs present good chemical compatibility, satisfactory thermochemical stability, and outstanding thermal management capability. In conclusion, the novel waste lotus shell-derived SSPCCs exhibit extensive potential for thermal management, such as heat recovery, solar energy conversion, and temperature regulation. This research not only introduces a promising avenue for enhancing sustainable materials in energy storage and conversion but also pioneers an innovative recycling strategy for waste lotus shells, thereby contributing to both environmental sustainability and efficient resource utilization.

Low-Frequency Resonant Magnetoelectric Effect in a Piezopolymer-Magnetoactive Elastomer Layered Structure at Different Magnetization Geometries.

The search for novel materials with enhanced characteristics for the advancement of flexible electronic devices and energy harvesting devices is currently a significant concern. Multiferroics are a prominent example of energy conversion materials. The magnetoelectric conversion in a flexible composite based on a piezopolymer layer and a magnetic elastomer layer was investigated. The study focused on investigating the dynamic magnetoelectric effect in various configurations of external alternating and constant homogeneous magnetic fields (L-T and T-T configurations). The T-T geometry exhibited a two orders of magnitude higher coefficient of the magnetoelectric effect compared to the L-T geometry. Mechanisms of structure bending in both geometries were proposed and discussed. A theory was put forward to explain the change in the resonance frequency in a uniform external field. A giant value of frequency tuning in a magnetic field of up to 362% was demonstrated; one of the highest values of the magnetoelectric effect yet recorded in polymer multiferroics was observed, reaching up to 134.3 V/(Oe∙cm).

Silica-Derived Nanostructured Electrode Materials for ORR, OER, HER, CO2RR Electrocatalysis, and Energy Storage Applications: A Review.

Silica-derived nanostructured catalysts (SDNCs) are a class of materials synthesized using nanocasting and templating techniques, which involve the sacrificial removal of a silica template to generate highly porous nanostructured materials. The surface of these nanostructures is functionalized with a variety of electrocatalytically active metal and non-metal atoms. SDNCs have attracted considerable attention due to their unique physicochemical properties, tunable electronic configuration, and microstructure. These properties make them highly efficient catalysts and promising electrode materials for next generation electrocatalysis, energy conversion, and energy storage technologies. The continued development of SDNCs is likely to lead to new and improved electrocatalysts and electrode materials. This review article provides a comprehensive overview of the recent advances in the development of SDNCs for electrocatalysis and energy storage applications. It analyzes 337,061 research articles published in the Web of Science (WoS) database up to December 2022 using the keywords "silica", "electrocatalysts", "ORR", "OER", "HER", "HOR", "CO2RR", "batteries", and "supercapacitors". The review discusses the application of SDNCs for oxygen reduction reaction (ORR), oxygen evolution reaction (OER), hydrogen evolution reaction (HER), carbon dioxide reduction reaction (CO2RR), supercapacitors, lithium-ion batteries, and thermal energy storage applications. It concludes by discussing the advantages and limitations of SDNCs for energy applications.

Strong Carbon Layer-Encapsulated Cobalt Tin Sulfide-Based Nanoporous Material as a Bifunctional Electrocatalyst for Zinc-Air Batteries.

Global demands for cost-effective, durable, highly active, and bifunctional catalysts for metal-air batteries are tremendously increasing in scientific research fields. In this work, a strategy for the rational fabrication of carbon layer-encapsulated cobalt tin sulfide nanopores (CoSnOH/S@C NPs) material as a bifunctional electrocatalyst for rechargeable zinc (Zn)-air batteries by a cost-effective and facile two-step hydrothermal method is reported. Moreover, the effect of metal elements on the morphology of CoSnOH nanodisks material via the hydrothermal method is investigated. Owing to its excellent nanostructure, exclusive porous network, and high specific surface area, the optimized CoSnOH/S@C NPs material reveals superior catalytic properties. The as-prepared CoSnOH/S@C NPs electrocatalyst reveals better properties of oxygen reduction reaction (half-wave potential of -0.88 V vs reversible hydrogen electrode) and oxygen evolution reaction (overpotential of 137mV at 10mAcm-2) when compared with commercial Pt/C and IrO2 catalyst materials. Most significantly, the CoSnO/S@C NPs-based Zn-air battery exhibits more excellent cycling stability than the Pt/C+IrO2 catalyst-based one. Consequently, the proposed material provides a new route for fabricating more active and stable multifunctional catalyst materials for energy conversion and storage systems.

Vacancies tailoring lattice anharmonicity of Zintl-type thermoelectrics

While phonon anharmonicity affects lattice thermal conductivity intrinsically and is difficult to be modified, controllable lattice defects routinely function only by scattering phonons extrinsically. Here, through a comprehensive study of crystal structure and lattice dynamics of Zintl-type Sr(Cu,Ag,Zn)Sb thermoelectric compounds using neutron scattering techniques and theoretical simulations, we show that the role of vacancies in suppressing lattice thermal conductivity could extend beyond defect scattering. The vacancies in Sr2ZnSb2 significantly enhance lattice anharmonicity, causing a giant softening and broadening of the entire phonon spectrum and, together with defect scattering, leading to a ~ 86% decrease in the maximum lattice thermal conductivity compared to SrCuSb. We show that this huge lattice change arises from charge density reconstruction, which undermines both interlayer and intralayer atomic bonding strength in the hierarchical structure. These microscopic insights demonstrate a promise of artificially tailoring phonon anharmonicity through lattice defect engineering to manipulate lattice thermal conductivity in the design of energy conversion materials.

Enhanced thermoelectric properties of Mg2Si0.3Sn0.7 via Bi-doping under high pressure

A series of n-type Mg2(Si0.3Sn0.7)1-xBix compounds with 0≤x≤0.02 were successfully synthesized through a combined approach involving solid-state reaction, high-pressure synthesis, and spark plasma sintering techniques. The method yielded homogeneously distributed single-phase materials at the micron scale, although minor compositional variations were detected within nanoscale precipitates embedded in the grains. The sample with Bi content of 0.01 exhibited enhanced thermoelectric properties, reaching a peak thermoelectric figure of merit (ZT) of 1.45 at 700 K while maintaining an average ZT of about 1.1 over the temperature range of 300−773 K. The enhancement in thermoelectric performance is ascribed to the optimized carrier concentration, band convergence, and refined microstructure. The findings suggest a simplified approach to doping that could be beneficial in creating high-performance thermoelectric materials for energy conversion.

Doping effects on the optoelectronic properties and the stability of Cs3Sb2I9: Density functional theory insights on photovoltaics and light-emitting devices

In this work, we address a knowledge gap regarding how cation and anion doping affect the stability and optoelectronic properties of Cs3Sb2I9 perovskites. We have employed Density Functional Theory (DFT) to investigate structures doped with Ag, In, Mo, Nb, Sc, Bi, Br and Cl in both 0D hexagonal P63/mmc and 2D trigonal P 3‾ m1 Cs3Sb2I9 polymorphs. Our results show that doping with either Sc, Bi, or In leads to negative decomposition energy and doping with Ag or In results in a reduced band gap while enhancing absorption, offering beneficial enhancements for LED and photovoltaic applications. Mo and Nb doping facilitate d-d transitions at lower energies, which is also significant for light emission applications. Conversely, halogen doping allows for fine-tuning the band gap with minimal changes in effective mass, accompanied by lattice parameter contraction, yielding more stable Sb-X bonds. Additionally, our analysis demonstrates that the 0D polymorph allows for easier dopant incorporation, leading to improved stability compared to the 2D structure. The results from this study offer important directions for experimentalists to explore in the development of efficient energy conversion materials.

Review: wood composites as sustainable energy conversion materials for efficient solar energy harvesting and light management

Review: wood composites as sustainable energy conversion materials for efficient solar energy harvesting and light management

Exploring anisotropic phases and spin transport in perovskite heterostructures: Insights into 3d/5d interfaces for antiferromagnetic spintronics

Transition metal oxides (TMOs) demonstrate a broad spectrum of properties encompassing electronic correlations, anisotropic transport, magnetism, and optical behavior. The anisotropy arises from both intrinsic crystal symmetry and extrinsic factors like epitaxial strain and structural asymmetry at TMO interfaces. Weiss and Neel's work has elucidated anisotropic magnetic behavior in antiferromagnetic (AFM) materials. AFM TMOs exhibit unique magnetotransport behavior, including weak antilocalization (WAL) and anisotropic magnetoresistance (AMR). Understanding the magnetic structure and band topology in AFM perovskites and their interfaces enables the tailored design of materials for spintronics and energy conversion. In few interfaces lacking inversion symmetry, Rashba spin–orbit coupling (SOC) induces WAL, a quantum correction in conductivity in a two-dimensional electronic system. Electron accumulation and charge transfer across 3d, 5d transition metal-based perovskite interfaces affect WAL and AMR, as observed in 3d/3d and 3d/5d AFM heterostructures, respectively. Advancements in spintronics rely on exploring spin-dependent transport anisotropy. This review focuses on various scattering mechanisms, categorized as extrinsic and intrinsic, in anisotropic transport, particularly in 3d/5d AFM superlattices. The WAL scattering mechanism depends on both intrinsic factors related to Rashba SOC-induced band topology and extrinsic sources like spin impurities and lattice ions. Moreover, the investigation into AMR mechanisms involves the application of impurity-based extrinsic scattering models, which are aligned with the Rashba and Dresselhauss models on Fermi surfaces. This exploration specifically targets the interface of two-band insulators, exemplified by LaAlO3/SrTiO3 and LaVO3/KTaO3. Furthermore, this model achieves comprehensive coverage, extending its applicability to 3d/5d AFM heterostructures like LaMnO3/SrIrO3 and CaMnO3/CaIrO3. Additionally, the intrinsic scattering mechanism tied to Berry phase effects related to band topology is studied, focusing on the CaMnO3/CaIrO3 superlattice. Despite manipulation challenges stemming from reduced stray fields, AFM materials show potential in interface physics and applications within the realm of spintronics.

Engineering surface dipoles on mixed conducting oxides with ultra-thin oxide decoration layers

Improving materials for energy conversion and storage devices is deeply connected with an optimization of their surfaces and surface modification is a promising strategy on the way to enhance modern energy technologies. This study shows that surface modification with ultra-thin oxide layers allows for a systematic tailoring of the surface dipole and the work function of mixed ionic and electronic conducting oxides, and it introduces the ionic potential of surface cations as a readily accessible descriptor for these effects. The combination of X-ray photoelectron spectroscopy (XPS) and density functional theory (DFT) illustrates that basic oxides with a lower ionic potential than the host material induce a positive surface charge and reduce the work function of the host material and vice versa. As a proof of concept that this strategy is widely applicable to tailor surface properties, we examined the effect of ultra-thin decoration layers on the oxygen exchange kinetics of pristine mixed conducting oxide thin films in very clean conditions by means of in-situ impedance spectroscopy during pulsed laser deposition (i-PLD). The study shows that basic decorations with a reduced surface work function lead to a substantial acceleration of the oxygen exchange on the surfaces of diverse materials.

Erbium doped samarium oxide nanoballs functionalized cluster surface as a robust electrocatalyst for efficient water oxidation

The oxygen evolution reaction (OER) is a crucial energy-storing and energy-changing half-process in water splitting. It is critical to expand the availability of renewable energy reservoirs, and effective electrodes must be robust and possess a high level of catalytic activity. However, it is difficult to eliminate overpotential and improve the performance of OER. In this study, Erbium (Er)-doped samarium oxide (Sm2O3) was synthesized by a facile co-precipitation technique. Using X-ray diffraction analysis, it was determined that a Sm2O3 cubic structure was formed when sharp peaks were observed. Using Fourier-transform infrared (FTIR spectroscopy) and scanning electron spectroscopy (SEM) pictures, the existence of Sm2O3 crystals was detected and surface geometry was observed. Energy dispersive X-ray (EDX) and X-ray photoelectron spectroscopy (XPS) confirm the successful Er doping in Sm2O3. The OER activities of pure Sm2O3 and Sm2O3 coupled with Er were determined using electrochemical. In comparison to pure Sm2O3, a high amount of Er-doped Sm2O3 possessed a low overpotential (365 mV for the OER) and a small Tafel slope (47 mV/dec). Consequently, OER became extremely active, metal oxide's structure and catalytic capabilities were altered by inclusion of rare earth metals. Erbium is an essential component when doped in Sm2O3 that improves the performance of OER. Among all 2% Er doped Sm2O3 is an excellent material for energy conversion.

Modeling thermoelectric figure of merit of BiCuSeO oxyselenide ceramic using extreme learning machine computational method

BiCuSeO ceramic is an eco-friendly oxyselenide thermoelectric material that provides alternative directions for refrigeration and power generation through direct conversion between electrical and thermal energy. Aside from environmental friendliness of BiCuSeO ceramic, relatively cheap input materials, low toxicity, good thermal and chemical stability are among the unique features that contribute significantly to wider applicability of this material for energy conversion. The energy conversion efficiency of un-doped and pristine BiCuSeO thermoelectric material is very low while enhancement of its energy conversion efficiency has attracted serious attention from both experimental and theoretical perspectives thorough modulation doping, dual-vacancies creation and dual doping among others. This work models the thermoelectric figure of merit (energy conversion efficiency, ECE) of doped BiCuSeO based ceramics using extreme learning machine (ELM) with ionic radii and elemental concentrations predictors. ECE-SNELM model with sine activation function performs better than ECE-SGELM with sigmoid activation function using root mean square error (RMSE), correlation coefficient (CC) and mean absolute error (MAE) performance evaluation and assessment parameters with improvement of 20.61 %, 5.51 % and 5.77 %, respectively when computed using testing samples of BiCuSeO-based ceramics. Comparison of the developed ECE-SNELM and ECE-SGELM model with the existing machine learning (ML) based model shows that ECE-SNELM and ECE-SGELM model respectively outperforms ML (2022) model with improvement of 70.89 % and 35.8 % using RMSE metric. The developed ECE-T-SNELM model that includes temperature among its descriptors further outperforms the existing ML based model with improvement of 39.39 % on the basis of RMSE metric. The predictions of the developed models agree well with the measured values. The developed ECE-SNELM was further employed for investigating the behavior of BiCuSeO-based ceramics after dopant incorporation. The precision demonstrated by the developed ECE-SNELM and ECE-SGELM models in determining thermoelectric figure of merit of BiCuSeO-based ceramics is highly commendable and meritorious in strengthen energy conversion efficiency of the ceramics for addressing the global challenges of energy crisis.

Thermal transport and thermoelectric properties of transition metal dichalcogenides MoX 2 from first-principles calculation

The properties of two-dimensional (2D) materials have been extensively studied and applied in various applications. Our interest is to theoretically investigate the thermal transport and thermoelectric properties of the 2D transition metal dichalcogenides MoX 2 (X=S, Se, Te). We employ density functional theory and Boltzmann transport theory with relaxation-time approximation to calculate the electronic and transport properties. We also implemented the kinetic-collective model to improve the calculation of lattice thermal conductivity. Our calculations indicate that MoTe2 has the highest ZT of 2.77 among the other MoX 2 at 550 K due to its low thermal conductivity and high electrical conductivity. Consequently, we suggest that MoX 2 monolayers hold promise as materials for energy conversion devices due to their relatively high ZT. Moreover, these results could be beneficial to design 2D material-based high-performance thermoelectric devices.

Control over Charge Separation by Imine Structural Isomerization in Covalent Organic Frameworks with Implications on CO2 Photoreduction.

Two-dimensional covalent organic frameworks (COFs) are an emerging class of photocatalytic materials for solar energy conversion. In this work, we report a pair of structurally isomeric COFs with reversed imine bond directions, which leads to drastic differences in their physical properties, photophysical behaviors, and photocatalytic CO2 reduction performance after incorporating a Re(bpy)(CO)3Cl molecular catalyst through bipyridyl units on the COF backbone (Re-COF). Using the combination of ultrafast spectroscopy and theory, we attributed these differences to the polarized nature of the imine bond that imparts a preferential direction to intramolecular charge transfer (ICT) upon photoexcitation, where the bipyridyl unit acts as an electron acceptor in the forward imine case (f-COF) and as an electron donor in the reverse imine case (r-COF). These interactions ultimately lead the Re-f-COF isomer to function as an efficient CO2 reduction photocatalyst, while the Re-r-COF isomer shows minimal photocatalytic activity. These findings not only reveal the essential role linker chemistry plays in COF photophysical and photocatalytic properties but also offer a unique opportunity to design photosensitizers that can selectively direct charges.

Nanostructured metal-oxide materials for solar energy absorption and conversion for industrial heater applications

As the most plentiful energy source on Earth, solar energy possesses the potential to fulfill all of humanity's energy requirements if harnessed to its full extent. Unlike finite fossil fuels, solar energy is a renewable resource that can be utilized indefinitely and does not contribute to climate change. The applicability of metal-oxides (TiO2) multi-ring resonator broad solar absorber (MOMRAB) for solar energy applications was examined in this work. A metal oxide layer and a multi-ring resonator structure combine to absorb sunlight at a variety of wavelengths (200 nm–900 nm) in the MOMRAB. While the metal oxide layer absorbs sunlight in the visible and infrared portions of the spectrum, the multi-ring resonator structure traps sunlight and lengthens its route within the MOMRAB. The MOMRAB is a promising material for a variety of applications due to its good absorptance (95.07 %) and polarization insensitivity across a wide wavelength range from 200 nm to 900 nm (700 nm). Along with examining the resonator's electric field, the research also included the polarization independence and incidence angle independence of the structure. Radiation barriers, solar induction systems, water and air warmers, and industrial heaters are a few possible uses for the MOMRAB. It is appropriate for space and satellite missions due to its zero transmittance and capacity to absorb a sizable amount of space radiation.

Harnessing visible light: enhancing TiO2 photocatalysis with photosensitizers for sustainable and efficient environmental solutions

The emerging field of using titanium dioxide (TiO2)-based photosensitizers for enhancing photocatalytic removal of thiazine dyes such as methylene blue (MB) from water has long been recognized for its exceptional photocatalytic properties, making it an attractive material for environmental remediation and energy conversion. However, its wide bandgap limits its responsiveness to visible light. As such, the utilization of TiO2-based photosensitizers for the removal of thiazine dyes, presents a promising avenue for diverse applications. In addressing the dual challenges of environmental pollution and harnessing sustainable energy sources, this review focuses on the removal of thiazine dyes from water and their subsequent application as photosensitizers for TiO2 materials. Thiazine dyes, ubiquitous in industrial effluents, pose environmental concerns due to their persistence and potential toxicity. Conversely, this innovative approach involves employing TiO2 materials as photocatalysts, utilizing the unique properties of thiazine dyes to enhance light absorption. Studies have shown that beyond the conventional role of thiazine dyes as colorants, they can serve as effective photosensitizers when coupled with TiO2. This tandem not only facilitates the elimination of thiazine dyes, such as MB, from water but also augments the improvement of the photocatalytic performance of TiO2 materials. The synergy between dye sensitizers and TiO2 enhances the overall efficiency of processes like dye degradation and water splitting. Dye sensitizers, acting as light energy absorbers, can efficiently transfer this energy to TiO2, thereby promoting electron transfer and generating reactive oxygen species (ROS). These ROS, in turn, initiate chemical reactions, rendering dye sensitizers valuable in applications such as wastewater treatment, solar energy conversion, and environmental remediation. As such, it is crucial to acknowledge the potential drawbacks associated with thiazine dyes, including toxicity and non-biodegradability. Consequently, careful consideration must be given to thiazine dye application and disposal. Therefore, this review manuscript delves into the comprehensive exploration of TiO2-based photosensitizers, shedding light on their efficacy in various photocatalytic processes for thiazine dye removal.

Two‐Dimensional Metallophthalocyanine Nanomaterials for Electrocatalytic Energy Conversion

Growing energy demand drives the rapid development of clean and reliable energy sources. In the past years, the exploration of novel materials with considerable efficiency and durability has drawn attention in the area of electrochemical energy conversion. Transition metal macrocyclic metallophthalocyanines (MPcs)‐based catalysts with a peculiar 2D constitution have emerged with a promising future account of their highly structural tailorability and molecular functionality which greatly extend their functionalities as electrocatalytic materials for energy conversion. This review summarizes the systematic engineering of synthesis of MPcs and their analogs in detail, and mostly pays attention to the frontier research of MPc‐based high‐performance catalysts toward different electrocatalytic processes concerning hydrogen, oxygen, water, carbon dioxide, and nitrogen, with a particular focus on discussing the interrelationship between the electrocatalytic activity and component/structure, as well as functional applications of MPcs. Finally, we give the gaps that need to be addressed after much thought.

Poly(dehydroalanine)-Based Hydrogels as Efficient Soft Matter Matrices for Light-Driven Catalysis.

Soft matter integration of photosensitizers and catalysts provides promising solutions to developing sustainable materials for energy conversion. Particularly, hydrogels bring unique benefits, such as spatial control and 3D-accessibility of molecular units, as well as recyclability. Herein, the preparation of polyampholyte hydrogels based on poly(dehydroalanine) (PDha) is reported. Chemically crosslinked PDha with bis-epoxy poly(ethylene glycol) leads to a transparent, self-supporting hydrogel. Due to the ionizable groups on PDha, this 3D polymeric matrix can be anionic, cationic, or zwitterionic depending on the pH value, and its high density of dynamic charges has a potential for electrostatic attachment of charged molecules. The integration of the cationic molecular photosensitizer [Ru(bpy)3 ]2+ (bpy = 2,2'-bipyridine) is realized, which is a reversible process controlled by pH, leading to light harvesting hydrogels. They are further combined with either a thiomolybdate catalyst ([Mo3 S13 ]2- ) for hydrogen evolution reaction (HER)or a cobalt polyoxometalate catalyst (Co4 POM = [Co4 (H2 O)2 (PW9 O34 )2 ]10- ) for oxygen evolution reaction (OER). Under the optimized condition, the resulting hydrogels show catalytic activity in both cases upon visible light irradiation. In the case of OER, higher photosensitizer stability is observed compared to homogeneous systems, as the polymer environment seems to influence decomposition pathways.

Organic Thin Films Enable Retaining the Oxidation State of Copper Catalysts during CO2 Electroreduction.

A key challenge in electrocatalysis remains controlling a catalyst's structural, chemical, and electrical properties under reaction conditions. While organic coatings showed promise for enhancing the selectivity and stability of catalysts for CO2 electroreduction (CO2RR), their impact on the chemical state of underlying metal electrodes has remained unclear. In this study, we show that organic thin films on polycrystalline copper (Cu) enable retaining Cu+ species at reducing potentials down to -1.0 V vs RHE, as evidenced by operando Raman and quasi in situ X-ray photoelectron spectroscopy. In situ electrochemical atomic force microscopy revealed the integrity of the porous organic film and nearly unaltered Cu electrode morphology. While the pristine thin film enhances the CO2-to-ethylene conversion, the addition of organic modifiers into electrolytes gives rise to improved CO2RR performance stability. Our findings showcase hybrid metal-organic systems as a versatile approach to control, beyond morphology and local environment, the oxidation states of catalysts and energy conversion materials.