Facile Surface Functionalization Research Articles

Construction of Frustrated Lewis Pairs in Poly(heptazine Imide) Nanosheets via Hydrogen Bonds for Boosting CO2 Photoreduction

AbstractThe creation of frustrated Lewis pairs on catalyst surface is an effective strategy for tuning CO2 activation. The critical step in the formation of frustrated Lewis pairs is the spatial effect of proximal Lewis acid‐Lewis base pairs. Here, we demonstrate a facile surface functionalization methodology that enables hydrogen bonding between N and H atoms to mediate the construction of frustrated Lewis pairs in poly(heptazine imide), thereby increasing the propensity to activate CO2 molecules. Experimental and theoretical results show that the construction of active hydrogen bonding regions can facilitate the bending of CO2 molecules. Furthermore, the delocalization of electron clouds induced by the hydrogen bonding‐mediated frustrated Lewis pairs can promote the heterolytic cleavage and photocatalytic conversion of CO2. This work highlights the potential of utilizing hydrogen bonding‐mediated strategy in heterogeneously photocatalytic activation of CO2 over polymer materials.

Construction of Frustrated Lewis Pairs in Poly(heptazine Imide) Nanosheets via Hydrogen Bonds for Boosting CO2 Photoreduction.

The creation of frustrated Lewis pairs on catalyst surface is an effective strategy for tuning CO2 activation. The critical step in the formation of frustrated Lewis pairs is the spatial effect of proximal Lewis acid-Lewis base pairs. Here, we demonstrate a facile surface functionalization methodology that enables hydrogen bonding between N and H atoms to mediate the construction of frustrated Lewis pairs in poly(heptazine imide), thereby increasing the propensity to activate CO2 molecules. Experimental and theoretical results show that the construction of active hydrogen bonding regions can facilitate the bending of CO2 molecules. Furthermore, the delocalization of electron clouds induced by the hydrogen bonding-mediated frustrated Lewis pairs can promote the heterolytic cleavage and photocatalytic conversion of CO2. This work highlights the potential of utilizing hydrogen bonding-mediated strategy in heterogeneously photocatalytic activation of CO2 over polymer materials.

Facile Surface Functionalization of Electrospun Elastic Nanofibers Via Initiated Chemical Vapor Deposition for Enhanced Neural Cell Adhesion and Alignment

Facile Surface Functionalization of Electrospun Elastic Nanofibers Via Initiated Chemical Vapor Deposition for Enhanced Neural Cell Adhesion and Alignment

Room-temperature phosphorescence of defect-engineered silica nanoparticles for high-contrast afterglow bioimaging

Room-temperature phosphorescence (RTP) has tremendous potential in optics and photonics. Unlike fluorescence, RTP has substantial afterglow signals even after the excitation light is removed, which allows for extended acquisition times and higher signal-to-noise ratio under time-gated bioimaging. However, conventional RTP materials, both metal-containing and metal-free organic compounds, typically have limited photostability and inherent toxicity, making them unsuitable for long-term biological applications. Here, we report metal- and organic fluorophore-free silica nanoparticles (SNPs) that facilitate long-lived phosphorescence and exhibit RTP for high-contrast bioimaging. Polycondensation of silicon precursors and silyl biphenyls forms biphenyl-doped SNPs (bSNPs), and thermal decomposition of biphenyl moieties generates optically active defects in the biphenyl-bonded silicate network. The calcined bSNPs (C-bSNPs) have RTP-related biphenyl defects composed of carbon impurities, corresponding to spectroscopic measurements and ab initio calculations. Facile surface functionalization of defect-engineered C-bSNPs with tumor-targeting peptides while maintaining long-lived RTP allows for tissue autofluorescence-free in vivo bioimaging for cancer diagnosis, surpassing the limitations of continuous-wave imaging.

Durable and Robust Antibacterial Polypropylene Hernia Mesh for Abdominal Wall Defect Repair.

Polypropylene (PP) mesh is commonly used in repairing abdominal wall hernia (AWH). However, the use of synthetic prosthesis comes with the risk of developing a prosthetic infection, resulting in delayed healing, secondary surgery, and potentially increased mortality. To address these issues, a facile surface functionalization strategy for PP mesh based on phytic acid (PA) and polyhexamethylene guanidine (PHMG) was constructed through a one-step co-deposition process, referred to as the PA/PHMG coating. The development of PA/PHMG coating is mainly attributed to the surface affinity of PA and the electrostatic interactions between PA and PHMG. The PA/PHMG coating could be completed within 4 h under mild conditions. The prepared PA/PHMG coatings on PP mesh surfaces exhibited desirable biocompatibility toward mammalian cells and excellent antibacterial properties against the notorious "superbug" methicillin-resistant Staphylococcus aureus (MRSA) and tetracycline-resistant Escherichia coli (TRE). The PA/PHMG-coated PP meshes showed killing ratios of over 99% against MRSA in an infected abdominal wall hernia repair model. Furthermore, histological and immunohistochemical analysis revealed a significantly attenuated degree of neutrophil infiltration in the PA/PHMG coating group, attributed to the decreased bacterial numbers alleviating the inflammatory response at the implant sites. Meanwhile, the pristine PP and PA/PHMG-coated meshes showed effective tissue repair, with the PA/PHMG coating group exhibiting enhanced angiogenesis compared with pristine PP meshes, suggesting superior tissue restoration. Additionally, PP meshes with the highest PHMG weight ratio (PA/PHMG(3)) exhibited excellent long-term robustness under phosphate-buffered saline (PBS) immersion with a killing ratio against MRSA still exceeding 95% after 60 days of PBS immersion. The present work provides a facile and promising approach for developing antibacterial implants.

Biofilm Inhibition on Medical Devices and Implants Using Carbon Dots: An Updated Review.

Biofilms are an intricate community of microbes that colonize solid surfaces, communicating via a quorum-sensing mechanism. These microbial aggregates secrete exopolysaccharides facilitating adhesion and conferring resistance to drugs and antimicrobial agents. The escalating global concern over biofilm-related infections on medical devices underscores the severe threat to human health. Carbon dots (CDs) have emerged as a promising substrate to combat microbes and disrupt biofilm matrices. Their numerous advantages such as facile surface functionalization and specific antimicrobial properties, position them as innovative anti-biofilm agents. Due to their minuscule size, CDs can penetrate microbial cells, inhibiting growth via cytoplasmic leakage, reactive oxygen species (ROS) generation, and genetic material fragmentation. Research has demonstrated the efficacy of CDs in inhibiting biofilms formed by key pathogenic bacteria such as Escherichia coli, Staphylococcus aureus, and Pseudomonas aeruginosa. Consequently, the development of CD-based coatings and hydrogels holds promise for eradicating biofilm formation, thereby enhancing treatment efficacy, reducing clinical expenses, and minimizing the need for implant revision surgeries. This review provides insights into the mechanisms of biofilm formation on implants, surveys major biofilm-forming pathogens and associated infections, and specifically highlights the anti-biofilm properties of CDs emphasizing their potential as coatings on medical implants.

Enhancing Efficiency and Stability in Carbon-Based Perovskite Solar Cells by Double Passivation with Ultralow-Cost Coal-Derived Graphene and Its Derivatives.

Coal-derived carbon nanomaterials possess numerous superior features compared to other classic carbon, such as readily accessible surfaces, tunable pore structure, and facile and precise surface functionalization. Therefore, the controllable preparation of coal-derived carbon nanomaterials is anticipated to be of great significance for the performance improvement and commercialization process of carbon-based perovskite solar cells (C-PSCs). In this study, we successfully synthesized highly stable and commercially valuable graphene oxide (GO) and reduced graphene oxide (rGO) utilizing coal. Compared to traditional methods and commercial graphene, the chemical oxidation and pyrolysis process used in this study is mild and simple, offering the advantages of controlled composition and the absence of other impurities. GO or rGO was incorporated into the top of the SnO2 electron transport layer (ETL) of C-PSCs. Under optimized conditions and ultraviolet-ozone (UVO) irradiation, the ultimate power conversion efficiency (PCE) increased from the unmodified 12.4 to 14.04% (based on rGO) and 15.18% (based on GO), representing improvements of 22 and 31%, respectively. The improved photovoltaic performance is mainly owing to enhanced charge transport capabilities, denser interfacial contacts, improved carrier separation properties, increased conductivity, and abundance of hydrophilic functional groups in GO, which can form more stable hydrogen bonds with SnO2. After being stored at room temperature and ambient humidity for 30 days, the modified, unpacked devices retained 87% of the highest power conversion efficiency (PCE). This study introduces a practical and manageable method to enhance the performance of C-PSCs by using functional carbon nanomaterials derived from coal.

Facile fabrication of Ti4+-immobilized magnetic nanoparticles by phase-transitioned lysozyme nanofilms for enrichment of phosphopeptides.

In this study, titanium (IV)-immobilized magnetic nanoparticles (Ti4+-PTL-MNPs) were firstly synthesized via a one-step aqueous self-assembly of lysozyme nanofilms for efficient phosphopeptide enrichment. Under physiological conditions, lysozymes readily self-organized into phase-transitioned lysozyme (PTL) nanofilms on Fe3O4@SiO2 and Fe3O4@C MNP surfaces with abundant functional groups, including -NH2, -COOH, -OH, and -SH, which can be used as multiple linkers to efficiently chelate Ti4+. The obtained Ti4+-PTL-MNPs possessed high sensitivity of 0.01 fmol μL-1 and remarkable selectivity even at a mass ratio of β-casein to BSA as low as 1:400 for phosphopeptide enrichment. Furthermore, the synthesized Ti4+-PTL-MNPs can also selectively identify low-abundance phosphopeptides from extremely complicated human serum samples and their rapid separation, good reproducibility, and excellent recovery were also proven. This one-step self-assembly of PTL nanofilms facilitated the facile and efficient surface functionalization of various nanoparticles for proteomes/peptidomes.

MXene-based composites in smart wound healing and dressings.

MXenes, a class of two-dimensional materials, exhibit considerable potential in wound healing and dressing applications due to their distinctive attributes, including biocompatibility, expansive specific surface area, hydrophilicity, excellent electrical conductivity, unique mechanical properties, facile surface functionalization, and tunable band gaps. These materials serve as a foundation for the development of advanced wound healing materials, offering multifunctional nanoplatforms with theranostic capabilities. Key advantages of MXene-based materials in wound healing and dressings encompass potent antibacterial properties, hemostatic potential, pro-proliferative attributes, photothermal effects, and facilitation of cell growth. So far, different types of MXene-based materials have been introduced with improved features for wound healing and dressing applications. This review covers the recent advancements in MXene-based wound healing and dressings, with a focus on their contributions to tissue regeneration, infection control, anti-inflammation, photothermal effects, and targeted therapeutic delivery. We also discussed the constraints and prospects for the future application of these nanocomposites in the context of wound healing/dressings.

Synthesis, properties and mechanism of carbon dots-based nano-antibacterial materials.

Antibiotics play an important role in the treatment of diseases, but bacterial resistance caused by their widespread and unreasonable use has become an urgent problem in clinical treatment. With the rapid advancement of nanoscience and nanotechnology, the development of nanomedicine has been transformed into a new approach to the problem of bacterial resistance. As a new type of carbon-based nanomaterial, carbon dots (CDs) have attracted the interest of antibacterial researchers due to their ease of preparation, amphiphilicity, facile surface functionalization, and excellent optical properties, among other properties. This article reviewed the synthesis methods and properties of various CDs and their composites in order to highlight the advancements in the field of CDs-based antibacterial agents. Then we focused on the relationship between the principal properties of CDs and the antibacterial mechanism, including the following: (1) the physical damage caused by the small size, amphiphilicity, and surface charge of CDs. (2) Photogenerated electron transfer characteristics of CDs that produce reactive oxygen species (ROS) in themselves or in other compounds. The ability of ROS to oxidize can lead to the lipid peroxidation of cell membranes, as well as damage proteins and DNA. (3) The nano-enzyme properties of CDs can catalyze reactions that generate ROS. (4) Synergistic antibacterial effect of CDs and antibiotics or other nanocomposites. Finally, we look forward to the challenges that CDs-based nanocomposites face in practical antibacterial applications and propose corresponding solutions to further expand the application potential of nanomaterials in the treatment of infectious diseases, particularly drug-resistant bacterial infections.

Combined Facile Synthesis, Purification, and Surface Functionalization Approach Yields Monodispersed Gold Nanorods for Drug Delivery Applications.

Synthesizing gold nanorods (AuNRs) by seed-mediated growth method results in the presence of undesired size and shape particles by-products occupying 10-90% of the population. In this study, AuNRs are synthesized by the seed-mediated growth method using cetyltrimethylammonium bromide (CTAB) as a surfactant. AuNRs with redshifted longitudinal localized surface plasmon resonance (LLSPR) peak, localized in the biological "transparency window" (650-1350nm), are synthesized after optimizing seed solution, silver nitrate solution, and hydrochloric acid solution volumes, based on the published protocols. A two-step purification method, dialysis followed by centrifugation, is applied to remove excess CTAB and collect LLSPR-redshifted AuNRs with high rod purity (>90%). CTAB is subsequently exchanged with polyethylene glycol (PEG) to improve AuNRs biocompatibility. PEGylated AuNRs are confirmed innocuous to both SN4741 cells and B16F10 cells by the modified MTT assay and the modified lactate dehydrogenase (LDH) assay up to 1nm and 24h incubation. In this study, a combined facile synthesis, purification, and surface functionalization approach is proposed to obtain water-dispersible monodispersed AuNRs for drug delivery applications.

Aptamer-modified metal organic frameworks for measurement of food contaminants: a review.

The measurement of food contaminants faces a great challenge owing to the increasing demand for safe food, increasing consumption of fast food, and rapidly changing patterns of human consumption. As different types of contaminants in food products can pose different levels of threat to human health, it is desirable to develop specific and rapid methods for their identification and quantification. During the past few years, metal-organic framework (MOF)-based materials have been extensively explored in the development of food safety sensors. MOFs are porous crystalline materials with tunable composition, dynamic porosity, and facile surface functionalization. The construction of high-performance biosensors for a range of applications (e.g., food safety, environmental monitoring, and biochemical diagnostics) can thus be promoted through the synergistic combination of MOFs with aptamers. Accordingly, this review article delineates recent innovations achieved for the aptamer-functionalized MOFs toward the detection of food contaminants. First, we describe the basic concepts involved in the detection of food contaminants in terms of the advantages and disadvantages of the commonly used analytical methods (e.g., DNA-based methods (PCR/real-time PCR/multiplex PCR/digital PCR) and protein-based methods (enzyme-linked immunosorbent assay/immunochromatography assay/immunosensor/mass spectrometry). Afterward, the progress in aptamer-functionalized MOF biosensors is discussed with respect to the sensing mechanisms (e.g., the role of MOFs as signal probes and carriers for loading signal probes) along with their performance evaluation (e.g., in terms of sensitivity). We finally discuss challenges and opportunities associated with the development of aptamer-functionalized MOFs for the measurement of food contaminants.

Interfacial shear strength of surface functionalized and functionalized CNT coated carbon fiber: A single fiber fragmentation study

The compatibility among nonpolar thermoplastics like polypropylene (PP) and carbon fibers (CF) having traditional sizing or coating is challenging. In this study, facile and effective surface functionalization of CF and its subsequent coating with functionalized carbon nanotubes (CNTs) were carried out to obtain improved interfacial shear strength (IFSS) which was validated by the single fiber fragmentation test (SFFT). Functional groups, -COOH, -OH, and -NH2, were separately grafted on the CF surface using different chemical routes. Additionally, ultrasonic assisted electrophoretic deposition (EPD) technique was used to coat -COOH, -OH, and -NH2 functionalized CNTs on the sized and surface functionalized CFs. Attenuated total reflection-infrared spectroscopy (ATR-IR), X-ray photoelectron spectroscopy (XPS), and field emission scanning electron microscopy (FE-SEM) images confirmed the successful surface functionalization and coating on CF. Neat PP and a blend of PP and maleic anhydride-grafted-styrene ethylene butylene styrene (MA-g-SEBS) were used as two different base polymer matrixes in preparing a total of 26 different SFFT samples. Silane functionalized CF coated with amine functionalized CNTs using ultrasonic assisted EPD process showed IFSS of ∼29 MPa which was an impressive ∼758% higher than pristine CF and highest among all the surface modified CFs. Interestingly, this translated into useful increase of ∼13% in single fiber tensile strength of functionalized and treated CF over and above that of as received CF.

Current Advances in Immunomodulatory Biomaterials for Cell Therapy and Tissue Engineering

AbstractBiomaterials have gained immense attention for various diseases due to their unique advantages over chemical drugs regarding cost, ease of production, toxicity, and therapeutic efficacy. However, these materials need an inert delivery system that locally delivers cells and minimally elicits foreign body response (FBR). In this aspect, various immunomodulatory biomaterials, including silk, collagen, fibrin, hyaluronic acid, and alginate‐based biomaterials, have great potential due to large natural sources, ease of extraction, low cost, chemical inertness, facile surface functionalization, long‐term polymeric stability, high biocompatibility, and fine tunability of biomaterials sizes and shapes. In this review article, the recent advancements in the biomedical applications of immunomodulatory biomaterials in different diseases, including diabetes, cancer, cardiovascular disease, bone regeneration, etc, are highlighted. Moreover, the FBR on immunomodulatory biomaterials is discussed and the current and future strategies for the potential mitigation of considerable immune responses toward immunomodulatory biomaterials and devices are highlighted.

Size effect of iron oxide nanorods with controlled aspect ratio on magneto-responsive behavior

Iron oxide (Fe3O4) has been widely used as a magnetic material for magnetorheological (MR) fluids due to its facile geometric control, magnetic properties, and surface functionalization. However, studies on controlling the aspect ratio of iron oxide nanoparticles applied to MR fluids have rarely been reported due to difficulties in preparing anisotropic magnetic particles. To gain insight into the application of anisotropic nanoparticle in MR fluids, in this work iron oxide nanorods are prepared by using β-FeOOH nanorods as a template. The size of the β-FeOOH nanorods is controlled by adding polyethyleneimine (PEI) as the size controlling agent, and further reduction results in iron oxide nanorods. The resulting iron oxide nanorods are uniform in size and shape and exhibit superparamagnetic properties and high magnetic saturation, which is suitable for MR applications. The influence of particle size of the iron oxide nanorods on MR properties is evaluated, and the result shows the MR fluids prepared with larger size nanorods exhibit higher shear stress due to the higher magnetic saturation ascribed to larger crystalline domain. Consequently, gaining control over the size and aspect ratio of the magnetic particles can lead to high performance MR fluids.

Recent Advances of NIR-II Emissive Semiconducting Polymer Dots for In Vivo Tumor Fluorescence Imaging and Theranostics.

Accurate diagnosis and treatment of tumors, one of the top global health problems, has always been the research focus of scientists and doctors. Near-infrared (NIR) emissive semiconducting polymers dots (Pdots) have demonstrated bright prospects in field of in vivo tumor fluorescence imaging owing to some of their intrinsic advantages, including good water-dispersibility, facile surface-functionalization, easily tunable optical properties, and good biocompatibility. During recent years, much effort has been devoted to developing Pdots with emission bands located in the second near-infrared (NIR-II, 1000-1700 nm) region, which hold great advantages of higher spatial resolution, better signal-to-background ratios (SBR), and deeper tissue penetration for solid-tumor imaging in comparison with the visible region (400-680 nm) and the first near-infrared (NIR-I, 680-900 nm) window, by virtue of the reduced tissue autofluorescence, minimal photon scattering, and low photon absorption. In this review, we mainly summarize the latest advances of NIR-II emissive semiconducting Pdots for in vivo tumor fluorescence imaging, including molecular engineering to improve the fluorescence quantum yields and surface functionalization to elevate the tumor-targeting capability. We also present several NIR-II theranostic Pdots used for integrated tumor fluorescence diagnosis and photothermal/photodynamic therapy. Finally, we give our perspectives on future developments in this field.

Artificial metalloenzyme with peroxidase-like activity based on periodic mesoporous organosilica with ionic-liquid framework

Artificial enzymes were developed as alternatives to natural enzymes. Considering the unique characteristics of periodic mesoporous organosilica (PMO) materials, a rational design approach was investigated to simulate the coordination sphere around the iron active center in natural horseradish peroxidase (HRP) and fabricate a new peroxidase-like nanozyme. Well-ordered mesoscopic structure, high surface area, tunable pore size, high thermal-hydrothermal stability, and facile surface functionalization are unique properties of PMOs which allow them be potential candidate for enzyme mimic catalysis. In the present study, a monofunctional PMO with ionic-liquid framework (PMO-IL) was prepared as a support to incorporate the iron protoporphyrin IX hemin. The interior surface of mesochannels were also modified by imidazole functional groups. The synthetic peroxidase-like nanomaterial was fully characterized using several techniques such as N2 adsorption-desorption analysis, Thermal gravimetric analysis (TGA), Fourier transform infrared spectroscopy (FTIR) spectroscopy, powder X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), high resolution transmission electron microscopy (HRTEM) and energy dispersive X-ray analysis (EDAX). Peroxidase-like activity of the current nanomaterial was evaluated using 2,2′-Azinobis [3-ethylbenzothiazoline-6-sulfonic acid]-diammonium salt (ABTS) in the presence of hydrogen peroxide in neutral pH condition. Michaelis-Menten kinetic parameters indicated enhanced affinity toward substrate. Results imply that the biomimetic pathways can be developed to achieve a new generation of nanozymes with excellent thermal stability and long-term storage stability which are promising as peroxidase mimics for various applications.

Zwitterionic Polymers toward the Development of Orientation-Sensitive Bioprobes

Dynamics with an orientational degree of freedom are fundamental in biological events. Probes with polarized luminescence enable a determination of the orientation. Lanthanide-doped nanocrystals can provide more precise analysis than quantum dots due to the nonphotoblinking/bleaching nature and the multiple line-shaped emission. However, the intrinsic polarization property of the original nanocrystals often deteriorates in complex physiological environments because the colloidal stability easily breaks and the probes aggregate in the media with abundant salts and macromolecules. Engineering the surface chemistry of the probes is thus essential to be compatible with biosystems, which has remained a challenging task that should be exclusively addressed for each specific probe. Here, we demonstrate a facile and efficient surface functionalization of lanthanide-doped nanorods by zwitterionic block copolymers. Due to the steric interaction and the intrinsic zwitterionic nature of the polymers, high colloidal stability of the zwitterionic nanorod suspension is achieved over wide ranges of pH and concentration of salts, even giving rise to the lyotropic liquid crystalline behavior of the nanorods in physiological media. The shear-aligned ability is shown to be unaltered by the coated polymers, and thus, the strongly polarized emission of Eu3+ is preserved. Besides, biological experiments reveal good biocompatibility of the zwitterionic nanorods with negligible nonspecific binding. This study is a stepping stone for the use of the nanorods as orientation probes in biofluids and validates the strategy of coupling zwitterions to lanthanide-doped nanocrystals for various bioapplications.

On the Versatility of Nanozeolite Linde Type L for Biomedical Applications: Zirconium-89 Radiolabeling and In Vivo Positron Emission Tomography Study.

Porous materials, such as zeolites, have great potential for biomedical applications, thanks to their ability to accommodate positively charged metal-ions and their facile surface functionalization. Although the latter aspect is important to endow the nanoparticles with chemical/colloidal stability and desired biological properties, the possibility for simple ion-exchange enables easy switching between imaging modalities and/or combination with therapy, depending on the envisioned application. In this study, the nanozeolite Linde type L (LTL) with already confirmed magnetic resonance imaging properties, generated by the paramagnetic gadolinium (GdIII) in the inner cavities, was successfully radiolabeled with a positron emission tomography (PET)-tracer zirconium-89 (89Zr). Thereby, exploiting 89Zr-chloride resulted in a slightly higher radiolabeling in the inner cavities compared to the commonly used 89Zr-oxalate, which apparently remained on the surface of LTL. Intravenous injection of PEGylated 89Zr/GdIII-LTL in healthy mice allowed for PET–computed tomography evaluation, revealing initial lung uptake followed by gradual migration of LTL to the liver and spleen. Ex vivo biodistribution confirmed the in vivo stability and integrity of the proposed multimodal probe by demonstrating the original metal/Si ratio being preserved in the organs. These findings reveal beneficial biological behavior of the nanozeolite LTL and hence open the door for follow-up theranostic studies by exploiting the immense variety of metal-based radioisotopes.

Carbene Ligands Enabled C–N Coupling for Methylamine Electrosynthesis: A Computational Study

Electrocatalytic conversion of carbon monoxide (CO) and nitric oxide (NO) into methylamine (MMA, CH3NH2) could convert excessive renewable energy and environmental pollutants into valuable chemicals. The main hurdle, however, is the inefficient C–N coupling as a result of the repulsive dipole–dipole interaction between adjacent coupling precursors. Herein, we report a simple strategy to weaken the repulsive dipole–dipole interaction using N-heterocyclic carbene to modify the pristine catalyst surface. The pristine catalyst for our study is MXene-doped with two Cu atoms using the O vacancy site of Mo2NO2 (Cu2@v-Mo2NO2). Our molecular modeling work based on density functional theory calculation discovered that surface-functionalized carbene ligands perturb the electronic configuration of chelated Cu sites, hence causing charge redistribution on the adsorbed reaction intermediates. Such charge redistribution successfully weakens the CO/NO dipole–dipole repulsion, effectively optimizes the binding strength of precursors, and leads to an effective C–N bond formation. Consequently, a pathway that selectively converts CO and NO to MMA with a facile C–N coupling step and low limiting potential is identified on the catalyst surface. Our work suggests a facile electrocatalyst surface functionalization strategy for the improved coupling between small-molecule precursors featuring dipole–dipole repulsion, with the potential to generalize to the sustainable synthesis of multi-carbon/nitrogen chemicals.