Multifunctional Polymer Research Articles

Multifunctional Polymer Interphase with Fast Kinetics for Ultrahigh‐rate Zn Metal Anode

Polymer interphase on Zn anodes obviates dendrite growth and side reactions, however has drawbacks of slow kinetics. Here, a multifunctional polymer interphase with fast kinectics is reported, using poly(phenazine‐alt‐pyromellitic anhydride) (PPPA) as an electrolyte additive. PPPA, with linear π‐conjugated structure and enriched polar pyridine (conjugated cyclic ‐C=N‐) and carbonyl (C=O) groups, preferentially absorbs on the Zn anode to form a stable solid‐electrolyte interpahse (SEI) layer in‐situ. The PPPA SEI is efficient to block direct contact between water molecules and Zn anode, and regulate the interfacial solvation structure and Zn depostion. Importantly, the expanding π‐conjugated structure of PPPA is shown to provide abundant 2D open channels for rapid Zn2+ transport, and the delocalized π electrons form a space electrostatic field to facilitate de‐solvation and diffusion of Zn2+. As a result, the Zn metal anode with PPPA/ZnSO4 electrolyte exhibits high Coulombic efficiency of 98.3% at current density of 20 mA cm−2, and excellent cycle lifespan for over 2000 cycles (400 h) at current density 50 mA cm−2 and plating/stripping capacity of 5 mAh cm−2. The Zn||MnO2 full battery exhibited a discharge capacity of 74.4 mAh g−1 after 5000 cycles at the current density of 2000 mA g−1, demonstrating practical feasibility.

Multifunctional Polymer Interphase with Fast Kinetics for Ultrahigh-rate Zn Metal Anode.

Polymer interphase on Zn anodes obviates dendrite growth and side reactions, however has drawbacks of slow kinetics. Here, a multifunctional polymer interphase with fast kinectics is reported, using poly(phenazine-alt-pyromellitic anhydride) (PPPA) as an electrolyte additive. PPPA, with linear π-conjugated structure and enriched polar pyridine (conjugated cyclic -C=N-) and carbonyl (C=O) groups, preferentially absorbs on the Zn anode to form a stable solid-electrolyte interpahse (SEI) layer in-situ. The PPPA SEI is efficient to block direct contact between water molecules and Zn anode, and regulate the interfacial solvation structure and Zn depostion. Importantly, the expanding π-conjugated structure of PPPA is shown to provide abundant 2D open channels for rapid Zn2+ transport, and the delocalized π electrons form a space electrostatic field to facilitate de-solvation and diffusion of Zn2+. As a result, the Zn metal anode with PPPA/ZnSO4 electrolyte exhibits high Coulombic efficiency of 98.3% at current density of 20 mA cm-2, and excellent cycle lifespan for over 2000 cycles (400 h) at current density 50 mA cm-2 and plating/stripping capacity of 5 mAh cm-2. The Zn||MnO2 full battery exhibited a discharge capacity of 74.4 mAh g-1 after 5000 cycles at the current density of 2000 mA g-1, demonstrating practical feasibility.

Multifunctional Polar Polymer Boosting PEO Electrolytes toward High Room Temperature Ionic Conductivity, High-Voltage Stability, and Excellent Elongation.

Poly(ethylene oxide) (PEO) has been widely studied as an electrolyte owing to its excellent lithium compatibility and good film-forming properties. However, its electrochemical performance at room temperature remains a significant challenge due to its low ionic conductivity, narrow electrochemical window, and continuous decomposition. Herein, we prepare a multifunctional polar polymer to optimize PEO's electrochemical properties and cycling stability. PEO's crystallinity is disrupted with the addition of polar polymer, and the amorphous polymer segments create more transfer pathways for Li-ion. More importantly, the polar groups enhance PEO's Li-ion transference number by facilitating lithium salt dissociation through Lewis acid-base interactions and weaken the coordination between Li-ion and ether oxygen, thereby expediting Li-ion migration. In addition, the trifluoromethyl groups promote TFSI- defluorination, forming LiF-rich solid electrolyte interphase layers that prevent continuous decomposition of PEO. The resulting composite electrolyte exhibits excellent room temperature ionic conductivity (2.06 × 10-4 S cm-1) and Li-ion transference number (0.30) and outstanding voltage (4.9 V). The assembled symmetric lithium battery could perform stably for 620 h at 0.1 mA cm-2. Li||LiFePO4 cells exhibit excellent capacity retention (87.81%) and Coulombic efficiency (100.0%) at 0.5 C over 700 cycles.

Progress in degradable polyurethane scaffolds with variable degradation rates for tissue engineering applications

AbstractGlobal catastrophic consequences associated with wars, natural disasters, and accidents are increasing day by day. Tissue engineering (TE) regenerate damaged tissues by using growth factors, cells, or three‐dimensional support biomaterials, that is, scaffolds. Scaffolds should degrade into resorbable, noncytotoxic, and excretable products in the physiological environment, along with successfully regenerating the damaged tissues. However, the requirement for scaffold degradation rate varies from patient to patient, depending on the nature, size, and cause of injuries. Thus, the synthesis and development of degradable scaffolds with focus toward variable degradation rates has become an engrossed research area. In this regard, multifunctional polymers such as polyurethane (PU) are suitable candidates. The degradation rate of PUs can be changed with the variations in the PU scaffold composition, such as the selection of the isocyanate, polyol, or the chain extender. This review will fill the research gap by analyzing the state‐of‐the‐art expansions of the degradable PU scaffolds with variable degradation rates based primarily on the selection and composition of polyol, isocyanate, and CE. It aims to guide the development of patient‐specific/customized scaffolds with appropriate scaffold degradation and tissue regeneration rates, along with the recommendations for future work.Highlights The requirement for scaffold degradation rate varies from patient to patient. There is a need to synthesize scaffolds with variable/tunable degradation rates. Multifunctional polymers such as polyurethanes (PUs) are suitable candidates. PUs degradation rate can be tuned via isocyanates, polyols and chain extenders.

Fluorinated multifunctional polymer vesicles for enhanced ocular surface penetration and synergistic treatment of dry eye disease.

Current pharmacotherapy for DED is limited by a vicious inflammatory cycle in which reactive oxygen species (ROS) play a critical role. Additionally, topical eye drop therapy for DED often suffers from poor ocular availability due to multiple ocular surface barriers. Considering the key role of the ROS-NLRP3-IL-1β signaling axis in DED, in this investigation, fluorinated multifunctional polymer vesicles were developed for enhanced ocular surface penetration and synergistic DED therapy by combining ROS scavenging and immunomodulation. MCC950, an NLRP3-IL-1β inhibitor, was loaded in situ during vesicle preparation. The results demonstrated that fluorocarbon units randomly distributed in the corona layer significantly enhanced ocular surface penetration. Furthermore, the vesicle membrane, composed of polyphenylborate ester blocks, efficiently scavenged excess ROS in inflamed corneal tissue. In response to excessive ROS, a hydrophobic-to-hydrophilic conversion of the vesicle membrane facilitated the efficient release of MCC950 to modulate the NLRP3-caspase-1-IL1β pathway. We believe that this work will provide insightful guidance to achieve effective treatment of DED by enhancing ocular surface penetration.

Solid Lipid Nanoparticles Coated with Glucosylated poly(2-oxazoline)s: A Supramolecular Toolbox Approach.

Multifunctional polymers are interesting substances for the formulation of drug molecules that cannot be administered in their pure form due to their pharmacokinetic profiles or side effects. Polymer-drug formulations can enhance pharmacological properties or create tissue specificity by encapsulating the drug into nanocontainers, or stabilizing nanoparticles for drug transport. We present the synthesis of multifunctional poly(2-ethyl-2-oxazoline-co-2-glyco-2-oxazoline)s containing two reactive end groups, and an additional hydrophobic anchor at one end of the molecule. These polymers were successfully used to stabilize (solid) lipid nanoparticles ((S)LNP) consisting of tetradecan-1-ol and cholesterol with their hydrophobic anchor. While the pure polymers interacted with GLUT1-expressing cell lines mainly based on their physicochemical properties, especially via interactions of the hydrophobic anchor with membranous compartments of the cells, LNP-cell interactions hinted toward an influence of the glucosylation on particle-cell interactions. The presented LNP are therefore promising systems for the delivery of drugs into GLUT1-expressing cell lines.

Multifunctional zinc silicate coating layer for high-performance aqueous zinc-ion batteries

Dendrite growth during the continuous charge/discharge process is a serious problem that leads to internal short circuits in aqueous zinc-ion batteries. Herein, a multifunctional zinc silicate polymer lithium polysilicate (LSO) was proposed to address the issues. LSO can prevent direct contact between electrolytes and zinc anodes, thereby suppressing severe dendrite growth. Its mechanically stable structure can restrain the stress release to further stabilize the electrode. In addition, LSO is chemically bonded to zinc anodes to ensure superior overall stability compared to other surface coatings. Moreover, LSO anodes exhibit outstanding electrolyte wettability and corrosion resistance, with strong adhesion properties. In-situ optical microscopy observation demonstrates its stability during charge/discharge process. Symmetrical cells using the Zn-LSO anode exhibited long cycling life of 833, 455, 344, and 260 h with low overpotentials of 66, 80, 118, and 141 mV at current densities of 0.5, 1, 3 and 5 mA cm-2, respectively. Full cells coupled with a MnO2 cathode showed a high-capacity reversibility of up to 234 mAh g-1 and outstanding rate performance at different current densities. This study demonstrates that LSO coating is a promising method for enhancing the electrochemical performance of zinc-ion batteries.

A Multi-Phase Analytical Model for Effective Electrical Conductivity of Polymer Matrix Composites Containing Micro-SiC Whiskers and Nano-Carbon Black Hybrids.

Multifunctional polymer composites containing micro/nano hybrid reinforcements have attracted intensive attention in the field of materials science and engineering. This paper develops a multi-phase analytical model for investigating the effective electrical conductivity of micro-silicon carbide (SiC) whisker/nano-carbon black (CB) polymer composites. First, CB nanoparticles are dispersed within the non-conducting epoxy to achieve a conductive CB-filled nanocomposite and its electrical conductivity is predicted. Some critical microstructures such as volume percentage and size of nanoparticles, and interphase characteristics surrounding the CB are micromechanically captured. Next, the electrical conductivity of randomly oriented SiC-containing composites in which the nanocomposite and whisker are considered as the matrix and reinforcement phases, respectively, is estimated. Influences of whisker aspect ratio and volume fraction on the effective electrical conductivity of the SiC/CB-containing polymer composites are explored. Some comparison studies are performed to validate the accuracy of the model. It is observed before the percolation threshold that the addition of nanoparticles with a uniform dispersion can improve the electrical conductivity of the polymer composites containing SiC/CB hybrids. Moreover, the results show that the electrical conductivity is more enhanced by the decrease in nanoparticle size. Interestingly, the composite percolation threshold is significantly reduced when SiC whiskers with a higher aspect ratio are added. This work will be favorable for the design of electro-conductive polymer composites with high performances.

Nonconventional Full-Color Luminescent Polyurethanes: Luminescence Mechanism at the Molecular Orbital Level.

The study of structure-activity relationships is a top priority in the development of nontraditional luminescent materials. In this work, nonconjugated polyurethanes (PUs) with full-color emission (red, green, and blue) are easily obtained by control of the diol monomer structure and the polymerization conditions. Selected diol monomers introduced single, double, or triple bond repeating units into the main chain of the PUs, in order to understand how unsaturated bonds and H-bonds affect their luminescence from a molecular orbital viewpoint. Detailed experimental and theoretical results show that the PUs have different temperature-dependent behaviors related to the interplay of H-bonding, through-space n-π interactions, and aggregation properties. The potential applications of PUs in colorful displays, covert information transmission, and multifunctional bioimaging have been verified. This work provides a new general protocol for the simple preparation of multifunctional nonconventional fluorescent polymers and deepens the understanding of their luminescence mechanisms.

Applications of polymeric nanoparticles in drug delivery for glioblastoma.

Glioblastoma (GBM) remains one of the most aggressive and treatment-resistant brain tumors, necessitating innovative therapeutic approaches. Polymer-based nanotechnology has emerged as a promising solution, offering precise drug delivery, enhanced blood-brain barrier (BBB) penetration, and adaptability to the tumor microenvironment (TME). This review explores the diverse applications of polymeric nanoparticles (NPs) in GBM treatment, including delivery of chemotherapeutics, targeted therapeutics, immunotherapeutics, and other agents for radiosensitization and photodynamic therapy. Recent advances in targeted delivery and multifunctional polymer highlight their potential to overcome the challenges that GBM brought, such as heterogeneity of the tumor, BBB limitation, immunosuppressive TME, and consideration of biocompatibility and safety. Meanwhile, the future directions to address these challenges are also proposed. By addressing these obstacles, polymer-based nanotechnology represents a transformative strategy for improving GBM treatment outcomes, paving the way for more effective and patient-specific therapies.

Construction of an ultrathin multi-functional polymer electrolyte for safe and stable all-solid-state batteries.

The ever-increasing demand for safe and high-energy-density batteries urges the exploration of ultrathin, lightweight solid electrolytes with high ionic conductivity. Solid polymer electrolytes (SPEs) with high flexibility, reduced interfacial resistance and excellent processability have been attracting significant attentions. However, reducing the thickness of SPEs to be comparable with that of commercial separators increases the risk of short-circuiting. Herein, an ultrathin (≈7 μm), flexible and mechanical robust SPE was constructed from a rationally designed multi-functional polymer network, i.e., poly[2,2,2-trifluoroethyl methacrylate-r-(2-ethylhexyl acrylate)-r-methyl methacrylate-r-1,4-bis(acryloyloxy)butane] (PTEM) and porous polyethylene (PE). The resultant PTEM@PE electrolyte possesses a high tensile strength of 128.0 MPa with extensibility up to 34.8%, which could effectively prevent short-circuiting and minimize the interfacial resistance of cells. The obtained all-solid-state Li|PTEM@PE|LiFePO4 cell exhibited stable cycling performance over 1500 cycles at 0.5 C with a capacity retention of 74.4%. With high-voltage NCM811 as the cathode, the cell fabricated with PTEM@PE showed a remarkable capacity retention of 84.2% over 500 cycles. Even with the high-mass loading (≈3 mA h cm-2) NCM811 cathode, the cell could be operated at ambient temperature, demonstrating superior ion-migration kinetics. The current design provides a promising strategy to develop ultrathin and multifunctional solid electrolytes for safe, long-cycling and high-energy-density all-solid-state batteries.

Self-template impregnated silver nanoparticles in coordination polymer gel: photocatalytic CO2 reduction, CO2 fixation, and antibacterial activity.

CO2 fixation and light-assisted conversion of CO2 in the presence of water into fuels and feedstocks are clean and sustainable techniques to alleviate the energy crisis and global climate change. In this regard, herein, a waterborne multifunctional metal-organic coordination polymer gel (Ag@GMP) was prepared from silver nitrate and guanosine 5'-monophosphate. Electron microscopy exhibits that Ag@GMP has a flower-like structure, which is composed of vertically grown sheets, and corresponding high magnification images display the presence of silver nanoparticles on the vertically grown sheets. Ag@GMP demonstrates remarkable photocatalytic performance, achieving a CO2 conversion rate of 18.6 μmol g-1 with approximately 85% selectivity towards CO at ambient temperature without using sacrificial agents. In situ diffuse reflectance infrared Fourier transform spectroscopy was employed to elucidate the proposed mechanism for photocatalytic CO2 reduction. Additionally, Ag@GMP exhibits significant catalytic activity in the fixation of CO2 with epoxides, leading to the formation of valuable chemicals under atmospheric pressure. Ag@GMP demonstrated efficient antibacterial activity against both Gram-negative and Gram-positive bacteria. The highest zone of inhibition was observed against S. aureus MTCC 3160 (15.83 ± 1.1 mm), and for E. coli, P. aeruginosa PAO1, and B. subtilis, it was found to be 12.66 ± 0.9, 14.33 ± 0.8 and 12.8 ± 0.8 mm, respectively.

“One-for-all” on-demand multifunctional fluorescent amphoteric polymers achieving breakthrough leather eco-manufacturing evolution

The proposed “all-in-one” strategy enables the creation of multifunctional materials for tanning, retanning, fatliquoring, and dyeing, simplifying leather manufacturing to meet market demands while delivering significant environmental benefits.

Development of multifunctional polymer composites with high red mud content

Red mud (RM) is one of the large-scale by-products of alumina production, posing significant environmental challenges due to its high alkalinity, toxicity, and substantial accumulation volumes. The object of this study is polymer composite based on styrene-butadiene aqueous dispersion with RM and chamotte (Pa2) as fillers at high concentrations (up to 90 wt. %). The primary problem addressed in this research is finding effective ways to utilize RM as secondary raw material to enhance its recycling efficiency and create multifunctional materials with adjustable properties. The study established that RM has an irregular plate-like structure with a high active surface area, which facilitates the formation of an open porous composite structure, while Pa2 forms a dense matrix due to its aluminosilicate content. Infrared spectral analysis confirmed the presence of functional groups (OH, Si–O, Al–O) that ensure the interaction of fillers with the polymer matrix. Thermogravimetric analysis demonstrated that RM and Pa2 exhibit similar behavior under heating. Mechanical tests revealed that RM-based composites exhibit high plasticity and energy absorption capacity, whereas Pa2-based composites are characterized by greater stiffness and strength (elastic modulus up to 129.8 MPa). The results indicate that the choice of filler type and concentration effectively regulates composite properties. The proposed approach enables the recycling of industrial waste and the development of multifunctional materials suitable for use in construction, protective coatings, and the production of structural elements capable of withstanding significant loads

Advances in interfacially engineered surface‐functionalized fillers for multifunctional polymer composite coatings

AbstractThe demand for multifunctional, high‐performance materials has driven advancements in surface‐functionalized fillers for polymer composite coatings. Despite progress, integrating multiple protective properties within a single hybrid formulation remains a challenge. This review explores recent developments in surface and interfacial engineering of biosourced fillers, including nanocellulose, and 2D materials like graphene oxide, MXenes, and layered double hydroxides, all of which have the potential to enhance the chemical resistance, mechanical strength, and thermal stability of polymer coatings. Key strategies include physical/chemical surface treatments, nanostructuring, and multiscale engineering to optimize cohesion, adhesion, and multivalent interactions among fillers, matrices, and substrates. The role of computational modeling in performance prediction and optimization is also discussed. The review concludes with current challenges and future directions, highlighting the importance of surface functionalization and interfacial engineering in developing next‐generation, multifunctional, and protective polymer coatings.Highlights Functionalized fillers boost polymer coatings' performance. 2D nanomaterials enhance coatings' resistance to corrosion, wear, and fire. Bio‐based fillers offer sustainable solutions for lightweight, robust coatings. Advanced interfacial engineering improves adhesion and coating durability. Modeling accelerates coating design by predicting interfacial interactions.

Scalable production of flexible and multifunctional graphene-based polymer composite film for high-performance electromagnetic interference shielding

Graphene have gained significant interest for potential in lightweight, ultrathin, and flexible electromagnetic interference (EMI) shielding materials due to their high electrical conductivity, low density, and ability to dissipate electromagnetic waves, but its poor dispersibility and processability hinders its applications. Besides, there is an urgent need for EMI shielding materials with multifunctional features. Herein, we proposed a flexible graphene/carbon nanotubes/polyurethane (GC/PU) composite film with a dense three-dimensional multilayer structure. This resultant GC/PU film shows high tensile strength of 42.9 MPa, ultra-high conductivity of 2087.2 S/m, and X-band EMI shielding efficiency of 37.7 dB at a thickness of 130 μm and even higher value of 72.1 dB at 520 μm. Moreover, this GC/PU film demonstrates an excellent electric heating performance (surface temperature of 127.5 °C at 5.0 V, thermal response <20 s) and flame-retardant capability, which endows it with the capability of anti-icing/de-icing. Therefore, this work may provide a promising approach for developing high-performance EMI shielding composites that may be used in the areas of wearables, defense, and aerospace.

Highly crystalline nanorods pyrene-based covalent organic framework artificial solid electrolyte interface accelerated interface Li+ regulation on lithium anode

The detrimental effects of heterogeneous Li deposition and aeolotropic Li dendrite propagation critically hamper its serviceability of Li metal batteries. The exploitation of neutral multifunctional porous polymer artificial SEI is imperative to modulate interfacial ionic transfer behavior. Herein, we propose a strategy based on dual-functional nanorod-shaped covalent organic frameworks (COF) to accelerate Li+ diffusion and mitigate lithium dendrite growth by creating an artificial solid electrolyte interface (SEI) layer. As anticipated, the immobilized high-polarity –OH and −CN- groups, along with the porous channel facilitates, facilitate uniform Li+ flux distribution and rapid Li+ migration. Additionally, the highly conjugated nature of the pyrene moiety not only enhances the plane π-π stacking crystallinity of TFDH-COF, but contributes positively to Li+ and repelling TFSI−. The combination of comprehensive ex-situ/in-situ characterizations and DFT calculations have unraveled the underlying mechanisms on the reductive Li mitigation energy barrier and enhancive Li+ transfer ability. In contrast with bare Li, the resultant TFDH-COF@Li electrode demonstrates the elevated reversibility of Li+ utilization, slight polarization, dendrite-free interface and prolonged cyclic performance in Li|Cu, Li|Li, and Li-based full cells operated at rigorous current densities. Those unswerving evidences enlighten the feasibility of engineering the neutrality COF layer to get rid of adverse disordered Li proliferation.

Construction of carbon nanotube-multifunctional porous ionic polymer core–shell nanocomposite for efficient conversion of carbon dioxide under co-catalyst free conditions

Metalated porous ionic polymers featuring multiple active sites show significant potential for carbon dioxide (CO2) fixation. However, general and efficient strategies to enhance their catalytic efficiency still remain to be developed. Herein, carbon nanotube-multifunctional ionic polymer core–shell composite (CNT@P(TBr-Py)-ZnBr2) was easily prepared by a solvothermal radical copolymerization strategy, followed by metallization with ZnBr2. Characterization revealed that the synthesized composite exhibited a distinct core–shell tubular nanostructure, with CNT serving as the core, and multifunctional polymer containing Lewis acid (Zn), nucleophilic Br¯ and CO2-philic triazine groups as the shell. Furthermore, the composite displayed broad pore size distribution and large average pore size. Impressively, CNT@P(TBr-Py)-ZnBr2 delivered an outstanding catalytic efficiency in the cycloaddition of CO2 to epichlorohydrin, surpassing the control catalysts poly(triazine-based vinyl ionic liquid) (PTBr), bipyridine-functionalized porous ionic polymer (P(TBr-Py), and ZnBr2 metalated P(TBr-Py) (P(TBr-Py)-ZnBr2) by factors of 5.4, 5.8, and 1.3, respectively. At 140 °C, a high turnover frequency (TOF) of 11174 h−1 and a 93.4 % yield of target cyclic carbonate were achieved in the absence of any additional co-catalyst. This exceptional catalytic performance of CNT@P(TBr-Py)-ZnBr2 can be mainly attributed to its unique core–shell structure, along with the synergistic catalytic effect of its multifunctional active sites. Also, the reaction can proceed smoothly under near-ambient conditions (30 °C, 1 bar CO2), though a longer reaction time was required. Additionally, CNT@P(TBr-Py)-ZnBr2 demonstrated a wide range of substrate compatibility and excellent recycling stability. This work therefore presents a viable approach for designing efficient and multifunctional ionic polymer-based catalysts for CO2 fixation.

Fabrication of polypropylene/carbon fiber/carbon black composite foam bonded with continuous carbon fiber reinforced polypropylene prepregs via high-pressure foam injection molding

The fabrication of polymer composite foams with several functions offers various advantages. Herein, we reported a highly efficient and mass-produced method for preparing polypropylene/carbon fiber/carbon black (PP/CF/CB) composite foams bonded with continuous CF reinforced PP prepregs. CFs were uniformly dispersed in PP via melt blending, but some agglomerations of CBs were observed owing to their little size. Compared with pure PP, the introduction of CB improved the thermal stability and flame retardance of composites. Owing to the homogeneity of polymer between composites and prepregs, they were well bonded by injection molding. The tensile strength of the samples bonded with prepregs was improved by 158.3–257.7 % for different filler contents. As CF and CB played the role of heterogeneous nucleation, and the high-pressure foam injection molding could easily tailor cellular structure by adjusting the holding time and mold temperature, composite foams bonded with two prepregs and with desired cells were successfully prepared. The injected foams with two prepregs had an enhanced electromagnetic interference shielding performance, which was 65.4 dB when the content was 10 wt% and 15 wt% for CF and CB, respectively. This work provides a universal approach for efficient and large-scale preparation of lightweight and multifunctional polymer composite foams.

Tracing the Structure-Activity Correlation in Cobalt-Doped Heteroatom-Enriched Nanoporous Material for CO2 Electroreduction

The electrochemical CO2 reduction reaction (CO2RR) to value added chemicals (CO, HCOOH, CH4, CH3OH, C2H5OH etc.) utilizing renewable energy sources has attracted considerable attention to close carbon cycle. [1,2] It has several advantages over other approaches such as 1) CO2 could be reduced under mild temperature and pressure conditions, 2) process could be controlled by adjusting the various reaction parameters such as potential etc., and 3) process is compact and feasible for scale up application. [1-3] However, this process has some limitations such as high overpotential, low selectivity & faradaic efficiency for products. Therefore, the designing of highly active electrocatalysts is required to improve catalytic efficiency. Among various reported catalysts, cobalt doped nitrogen enriched materials with atomically dispersed Co–N sites have displayed superior activities and selectivity in electrochemical process for the reduction of CO2. [1-4] However, the effect of synthesis conditions and composition of active species on product selectivity is not rigorously studied yet.In this research, a series of Co-doped multifunctional nitrogen-enriched nanoporous polymer (n-Co@MNENP) with amine and hydroxyl functionalities has been synthesized by condensation of 2-hydroxy-1,3,5-benzenetricarbaldehyde and melamine with calculated amount of cobalt chloride hexahydrate for incorporating n% (n = 10, 50 and 100) of Co content followed by pyrolysis at temperature 550 (designated as n-Co@MNENP-550) and 700 °C (designated as n-Co@MNENP-700). The structure of the synthesized in-situ and pyrolyzed specimens was confirmed by spectroscopic investigations such as FT-IR, and XPS. The Co content was estimated from ICP analysis. The thermal stability of the specimen was investigated using TGA/DTG. The FE-SEM and EDAX revealed almost spherical agglomerated nanoparticles with homogeneous distribution of Co species. PDF and total scattering (TS) analysis confirmed the presence of Co-N species in 10% and 100% samples while 50% sample has metallic Co(fcc/hcp) and CoO/N active species. Further, synthesized specimens have been explored for CO2RR. Among all the electrocatalysts, n-Co@MNENP-700 have shown the higher activity in CO2RR in which 10-Co@MNENP-700 and 100-Co@MNENP-700 could only produce CO, while 50-Co@MNENP-700 results in CO and C2H5OH production. These results reveal that atomically dispersed cobalt–nitrogen sites are responsible for CO generation while CoO, metallic Co species in combination with Co-N sites are responsible for CO and C2H5OH generation which confirmed that the compositions of Co-based catalysts greatly influence CO2RR activity and selectivity.