Surface Chemistry Research Articles

A Bio-Inspired Multifunctional Hydrogel Network with Toughly Interfacial Chemistry for Highly Reversible Flexible Zinc Batteries.

Flexible and high-performance aqueous Zn-ion batteries (ZIBs), coupled with low cost and safe, are considered as one of the most promising energy storage candidates for wearable electronics. However, most of hydrogel electrolytes suffer from poor mechanical properties and interfacial chemistry, which limits them to suppressed performance levels in flexible ZIBs, especially under harsh mechanical strains. Herein, a bio-inspired multifunctional hydrogel electrolyte network (polyacrylamide (PAM)/trehalose) with improved mechanical and adhesive properties was developed via a simple trehalose network-repairing strategy to stabilize the interfacial chemistry for highly reversible flexible ZIBs. As a result, the trehalose-modified PAM hydrogel exhibits a superior strength and stretchability up to 100 kPa and 5338%, respectively, as well as strong adhesive properties to various substrates. Also, the PAM/trehalose hydrogel electrolyte provides superior anti-corrosion capability for Zn anode and regulates Zn nucleation/growth, resulting in achieving a high Coulombic efficiency of 98.8%, and long-term stability over 2400 h. Importantly, the flexible Zn//MnO2 pouch cell exhibits excellent cycling performance under different bending conditions, which offers a great potential in flexible energy-related applications and beyond.

Low Contact Resistance on Monolayer MoS2 Field-Effect Transistors Achieved by CMOS-Compatible Metal Contacts.

Contact engineering on monolayer layer (ML) semiconducting transition metal dichalcogenides (TMDs) is considered the most challenging problem toward using these materials as a transistor channel in future advanced technology nodes. The typically observed strong Fermi-level pinning induced in part by the reaction of the source/drain contact metal and the ML TMD frequently results in a large Schottky barrier height, which limits the electrical performance of ML TMD field-effect transistors (FETs). However, at a microscopic level, little is known about how interface defects or reaction sites impact the electrical performance of ML TMD FETs. In this work, we have performed statistically meaningful electrical measurements on at least 120 FETs combined with careful surface analysis to unveil contact resistance dependence on interface chemistry. In particular, we achieved a low contact resistance for ML MoS2 FETs with ultrahigh-vacuum (UHV, 3 × 10-11 mbar) deposited Ni contacts, ∼500 Ω·μm, which is 5 times lower than the contact resistance achieved when deposited under high-vacuum (HV, 3 × 10-6 mbar) conditions. These electrical results strongly correlate with our surface analysis observations. X-ray photoelectron spectroscopy (XPS) revealed significant bonding species between Ni and MoS2 under UHV conditions compared to that under HV. We also studied the Bi/MoS2 interface under UHV and HV deposition conditions. Different from the case of Ni, we do not observe a difference in contact resistance or interface chemistry between contacts deposited under UHV and HV. Finally, this article also explores the thermal stability and reliability of the two contact metals employed here.

Bionano Interactions of Organosilica Nanoparticles with Myeloid Derived Immune Cells.

Investigating the interactions between nanomaterials and the cells they are likely to encounter in vivo is a critical aspect of designing nanomedicines for imaging and therapeutic applications. Immune cells such as dendritic cells, macrophages, and myeloid derived suppressor cells have a frontline role in the identification and removal of foreign materials from the body, with interactions shown to be heavily dependent on variables such as nanoparticle size, charge, and surface chemistry. Interactions such as cellular association or uptake of nanoparticles can lead to diminished functionality or rapid clearance from the body, making it critical to consider these interactions when designing and synthesizing nanomaterials for biomedical applications ranging from drug delivery to imaging and biosensing. We investigated the interactions between PEGylated organosilica nanoparticles and naturally endocytic immune cells grown from stem cells in murine bone marrow. Specifically, we varied the particle size from 60 nm up to 1000 nm and investigated the effects of size on immune cell association, activation, and maturation with these critical gatekeeper cells. These results will help inform future design parameters for in vitro and in vivo biomedical applications utilizing organosilica nanoparticles.

Photoelectrochemistry of Redox-Active Self-Assembled Monolayers Formed on n-Si/Au Nanoparticle Photoelectrodes.

Controlling the chemistry of the electrode-solution interface is critically important for applications in sensing, energy storage, corrosion prevention, molecular electronics, and surface patterning. While numerous methods of chemically modifying electrodes exist, self-assembled monolayers (SAMs) containing redox-active moieties are particularly important because they are easy to prepare, have well-defined interfaces, and can exhibit textbook photoelectrochemistry. Here, we investigate the photoelectrochemistry of redox-active SAMs on semiconductor/metal interfaces, where the SAM is attached to the metal site instead of the semiconductor. n-Si/Au photoelectrodes were fabricated using a benchtop electrodeposition procedure and subsequently modified by immersion in aqueous solutions of (ferrocenyl)hexanethiol and mercaptohexanol. We explored the relevant preparation conditions, finding that after optimization, we were able to obtain canonical cyclic voltammetry for a surface-bound redox molecule that could be turned on and off using light. We then characterized the optimized electrodes under varying illumination intensities, finding that the heterogeneous electron transfer kinetics improved under higher illumination intensities. These results lay the foundation for future studies of semiconductor/metal/molecule interfaces relevant to sensing and electrocatalysis.

Multifold topological semimetals

Abstract The discovery of topological semimetals with multifold band crossings has opened up a new and
exciting frontier in the field of topological physics. These materials exhibit large Chern numbers, leading
to long double Fermi arcs on their surfaces, which are protected by either crystal symmetries or topological
order. The impact of these multifold crossings extends beyond surface science, as they are not constrained
by the Poincar´e classification of quasiparticles and only need to respect the crystal symmetry of one of
the 1651 magnetic space groups. Consequently, we observe the emergence of free fermionic excitations
in solid-state systems that have no high-energy counterparts, protected by non-symmorphic symmetries.
In this work, we review the recent theoretical and experimental progress made in the field of multifold
topological semimetals. We begin with the theoretical prediction of the so-called multifold fermions and
discuss the subsequent discoveries of chiral and magnetic topological semimetals. Several experiments that
have realized chiral semimetals in spectroscopic measurements are described, and we discuss the future
prospects of this field. These exciting developments have the potential to deepen our understanding of the
fundamental properties of quantum matter and inspire new technological applications in the future.

Reconfigurable Optical Sensor for Metal-Ion-Mediated Label-Free Recognition of Different Biomolecular Targets.

Reconfiguration of chemical sensors, intended as the capacity of the sensor to adapt to novel operational scenarios, e.g., new target analytes, is potentially game changing and would enable rapid and cost-effective reaction to dynamic changes occurring at healthcare, environmental, and industrial levels. Yet, it is still a challenge, and rare examples of sensor reconfiguration have been reported to date. Here, we report on a reconfigurable label-free optical sensor leveraging the versatile immobilization of metal ions through a chelating agent on a nanostructured porous silica (PSiO2) optical transducer for the detection of different biomolecules. First, we show the reversible grafting of different metal ions on the PSiO2 surface, namely, Ni2+, Cu2+, Zn2+, and Fe3+, which can mediate the interaction with different biomolecules and be switched under mild conditions. Then, we demonstrate reconfiguration of the sensor at two levels: 1) switching of the metal ions on the PSiO2 surface from Cu2+ to Zn2+ and testing the ability of Cu2+-functionalized and Zn2+-reconfigured devices for the sensing of the dipeptide carnosine (CAR), leveraging the well-known chelating ability of CAR toward divalent metal ions; and 2) reconfiguration of the Cu2+-functionalized PSiO2 sensor for a different target analyte, namely, the nucleotide adenosine triphosphate (ATP), switching Cu2+ with Fe3+ ions to exploit the interaction with ATP through phosphate groups. The Cu2+-functionalized and Zn2+-reconfigured sensors show effective sensing performance in CAR detection, also evaluated in tissue samples from murine brain, and so does the Fe3+-reconfigured sensor toward ATP, thus demonstrating effective reconfiguration of the sensor with the proposed surface chemistry.

Green synthesis of magnetite iron oxide nanoparticles using Azadirachta indica leaf extract loaded on reduced graphene oxide and degradation of methylene blue

In the current arena, new-generation functional nanomaterials are the key players for smart solutions and applications including environmental decontamination of pollutants. Among the plethora of new-generation nanomaterials, graphene-based nanomaterials and nanocomposites are in the driving seat surpassing their counterparts due to their unique physicochemical characteristics and superior surface chemistry. The purpose of the present research was to synthesize and characterize magnetite iron oxide/reduced graphene oxide nanocomposites (FeNPs/rGO) via a green approach and test its application in the degradation of methylene blue. The modified Hummer's protocol was adopted to synthesize graphene oxide (GO) through a chemical exfoliation approach using a graphitic route. Leaf extract of Azadirachta indica was used as a green reducing agent to reduce GO into reduced graphene oxide (rGO). Then, using the green deposition approach and Azadirachta indica leaf extract, a nanocomposite comprising magnetite iron oxides and reduced graphene oxide i.e., FeNPs/rGO was synthesized. During the synthesis of functionalized FeNPs/rGO, Azadirachta indica leaf extract acted as a reducing, capping, and stabilizing agent. The final synthesized materials were characterized and analyzed using an array of techniques such as scanning electron microscopy (SEM)-energy dispersive X-ray microanalysis (EDX), Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction analysis, and UV–visible spectrophotometry. The UV–visible spectrum was used to evaluate the optical characteristics and band gap. Using the FT-IR spectrum, functional groupings were identified in the synthesized graphene-based nanomaterials and nanocomposites. The morphology and elemental analysis of nanomaterials and nanocomposites synthesized via the green deposition process were investigated using SEM–EDX. The GO, rGO, FeNPs, and FeNPs/rGO showed maximum absorption at 232, 265, 395, and 405 nm, respectively. FTIR spectrum showed different functional groups (OH, COOH, C=O), C–O–C) modifying material surfaces. Based on Debye Sherrer's equation, the mean calculated particle size of all synthesized materials was < 100 nm (GO = 60–80, rGO = 90–95, FeNPs = 70–90, Fe/GO = 40–60, and Fe/rGO = 80–85 nm). Graphene-based nanomaterials displayed rough surfaces with clustered and spherical shapes and EDX analysis confirmed the presence of both iron and oxygen in all the nanocomposites. The final nanocomposites produced via the synthetic process degraded approximately 74% of methylene blue. Based on the results, it is plausible to conclude that synthesized FeNPs/rGO nanocomposites can also be used as a potential photocatalyst degrader for other different dye pollutants due to their lower band gap.

Patterned PVA Hydrogels with 3D Petri Dish® Micro-Molds of Varying Topography for Spheroid Formation of HeLa Cancer Cells: In Vitro Assessment

Cell spheroids are an important three-dimensional (3D) model for in vitro testing and are gaining interest for their use in clinical applications. More natural 3D cell culture environments that support cell–cell interactions have been created for cancer drug discovery and therapy applications, such as the scaffold-free 3D Petri Dish® technology. This technology uses reusable and autoclavable silicone micro-molds with different topographies, and it conventionally uses gelled agarose for hydrogel formation to preserve the topography of the selected micro-mold. The present study investigated the feasibility of using a patterned Poly(vinyl alcohol) hydrogel using the circular topography 12–81 (9 × 9 wells) micro-mold to form HeLa cancer cell spheroids and compare them with the formed spheroids using agarose hydrogels. PVA hydrogels showed a slightly softer, springier, and stickier texture than agarose hydrogels. After preparation, Fourier transform infrared (FTIR) spectra showed chemical interactions through hydrogen bonding in the PVA and agarose hydrogels. Both types of hydrogels favor the formation of large HeLa spheroids with an average diameter of around 700–800 µm after 72 h. However, the PVA spheroids are more compact than those from agarose, suggesting a potential influence of micro-mold surface chemistry on cell behavior and spheroid formation. This was additionally confirmed by evaluating the spheroid size, morphology, integrity, as well as E-cadherin and Ki67 expression. The results suggest that PVA promotes stronger cell-to-cell interactions in the spheroids. Even the integrity of PVA spheroids was maintained after exposure to the drug cisplatin. In conclusion, the patterned PVA hydrogels were successfully prepared using the 3D Petri Dish® micro-molds, and they could be used as suitable platforms for studying cell–cell interactions in cancer drug therapy.

Effect of Stainless Steel Substrate Preparation on the Adhesion Strength and Morphology of Electrophoretically Deposited Sodium Alginate Coatings

AbstractIn this study, the influence of various mechanical and chemical surface treatments on the adhesion strength and surface properties of sodium alginate coatings electrophoretically deposited (EPD) on 316L stainless steel substrates was investigated. XPS and TEM results revealed the presence of oxide layers containing elements from the substrates, with thicknesses varying from 1 to 45 nm, depending on the treatment used. Most substrates exhibited high roughness and hydrophilic properties (CA with water 62.8–82.6 deg). Sodium alginate coatings with uniform morphology were deposited with the same process parameters, i.e., 5 V and 300 s. The surface topography of the coatings was closely related to that of the substrate on which they were deposited. All coatings exhibited higher hydrophilicity (CA with water 29.5–49.7 deg) compared to the substrates (CA with water 62.8–82.6 deg). The coatings on the etched and anodized substrates demonstrated the highest adhesion strength (class 4B), attributed to the very low oxide layer thickness and the specific substrate surface topography. Mechanical interlocking was identified as the primary adhesion mechanism for these coatings. This work provides insight into optimizing surface treatments for improved adhesion of sodium alginate coatings to stainless steel substrates widely used for temporary bone implants. The results obtained will also be helpful in providing high adhesion of sodium alginate-based composite coatings to steel substrates.

Asymmetric Hydrogel Electrolyte Featuring a Customized Anode and Cathode Interfacial Chemistry for Advanced Zn-I2 Batteries.

An integrated asymmetric hydrogel electrolyte with a tailored composition and chemical structure on the cathode/anode-electrolyte interface is designed to boost the cost-effective, high-energy Zn-I2 battery. Such a configuration concurrently addresses the parasitic reactions on the Zn anode side and the polyiodide shuttle issue afflicting the cathode. Specifically, the Zn2+-cross-linked sodium alginate and carrageenan dual network (Carra-Zn-Alg) is adopted to guide the Zn2+ transport, achieving a dendrite-free morphology on the Zn surface and ensuring long-term stability. For the cathode side, the poly(vinyl alcohol)-strengthened poly(3,4-ethylenedioxythiophene)polystyrenesulfonate hydrogel (PVA-PEDOT) with high conductivity is employed to trap polyiodide and accelerate electron transfer for mitigating the shuttle effect and facilitating I2/I- redox kinetics. Attributing to the asymmetrical architecture with a customized interfacial chemistry, the optimized Zn-I2 cell exhibits a superior Coulombic efficiency of 99.84% with a negligible capacity degradation at 0.1 A g-1 and an enhanced stability of 10 000 cycles at 5 A g-1. The proposed asymmetric hydrogel provides a promising route to simultaneously resolve the distinct challenges encountered by the cathode and anode interfaces in rechargeable batteries.

Crystalline Metal-Organic Framework Coatings Engineered via Metal-Phenolic Network Interfaces.

Crystalline metal-organic frameworks (MOFs) have garnered extensive attention owing to their highly ordered porous structure and physicochemical properties. However, their practical application often requires their integration with various substrates, which is challenging because of their weakly adhesive nature and the diversity of substrates that exhibit different properties. Herein, we report the use of amorphous metal-phenolic network coatings to facilitate the growth of crystalline MOF coatings on various particle and planar substrates. Crystalline MOFs with different metal ions and morphologies were successfully deposited on substrates (13 types) of varying sizes, shapes, and surface chemistries. Furthermore, the physicochemical properties of the coated crystalline MOFs (e.g., composition, thickness) could be tuned using different synthesis conditions. The engineered MOF-coated membranes demonstrated excellent liquid and gas separation performance, exhibiting a high H2 permeance of 63200 GPU and a H2/CH4 selectivity of 10.19, likely attributable to the thin nature of the coating (~180 nm). Considering the vast array of MOFs available (>90,000) and the diversity of substrates, this work is expected to pave the way for creating a wide range of MOF composites and coatings with potential applications in diverse fields.

Pistia stratiotes L. Biochar for Sorptive Removal of Aqueous Inorganic Nitrogen

Biochar has proven effective in the remediation of excess nitrogen from soil and water. Excess nitrogen from agricultural fields ends up in aquatic systems and leads to reduced water quality and the proliferation of invasive species. This study aimed to assess the efficiency of chemically surface-modified biochar produced from invasive Pistia stratiotes L. for the adsorption of inorganic nitrogen (NH4+ and NO3−). Biochar structure was investigated using scanning electron microscopy, energy-dispersive X-ray analysis, X-ray photoelectron spectroscopy, Fourier-transform infrared spectroscopy, and inductively coupled plasma mass spectrometry. The results from adsorption experiments indicate that NH4+ removal was optimal (0.8–1.3 mg N g−1) at near-neutral pH levels (6.0–7.5), while NO3− removal was optimal (0.4–0.8 mg N g−1) under acidic pH conditions (4.8–6.5) using the modified biochar. These findings highlight the significance of solution pH, biochar morphology, and surface chemistry in influencing the adsorption of NH4+ and NO3−. However, further studies are necessary to assess the potential oxidative transformation of NH4+ to NO3− by biochar, which might have contributed to the reduction in NH4+ in the aqueous phase.

Rechargeable Seawater-Based Chloride-Ion Batteries Enabled by Covalent Surface Chemistry in MXenes.

Rechargeable aqueous chloride-ion batteries (ACIBs) using Cl- ions as charge carriers represent a promising energy-storage technology, especially when natural seawater is introduced as the electrolyte, which can bring remarkable advantages in terms of cost-effectiveness, safety, and environmental sustainability. However, the implementation of this technology is hindered by the scarcity of electrodes capable of reversible chloride-anion storage. Here, we show that a Ti3C2Clx MXene with Cl surface terminations enables reversible Cl- ion storage in aqueous electrolytes. Further, we developed seawater-based ACIBs that show a high specific capacity and an exceptionally long lifespan (40000 cycles, more than 1 year) in natural seawater electrolyte. The pouch-type cells achieve a high energy density (50 Wh Lcell-1) and maintain stable performance across a broad temperature range (-20 to 50 °C). Our investigations reveal that the covalent interaction between Cl- ions and Cl-terminated MXene facilitates Cl- ion intercalation into the MXene interlayer, promoting rapid ion migration with a low energy barrier (0.10 eV). Moreover, this MXene variant also enables the reversible storage of Br- ions in an aqueous electrolyte with a long cycle life. This study may advance the design of anion storage electrodes and enable the development of sustainable aqueous batteries.

Correction to “Synthesis, Surface Chemistry, and Fluorescent Properties of InP Quantum Dots”

Correction to “Synthesis, Surface Chemistry, and Fluorescent Properties of InP Quantum Dots”

MolGC: molecular geometry comparator algorithm for bond length mean absolute error computation on molecules.

Density Functional Theory (DFT) is extensively used in theoretical and computational chemistry to study molecular and crystal properties across diverse fields, including quantum chemistry, materials physics, catalysis, biochemistry, and surface science. Despite advances in DFT hardware and software for optimized geometries, achieving consensus in molecular structure comparisons with experimental counterparts remains a challenge. This difficulty is exacerbated by the lack of automated bond length comparison tools, resulting in labor-intensive and error-prone manual processes. To address these challenges, we propose MolGC, a Molecular Geometry Comparator algorithm that automates the comparison of optimized geometries from different theoretical levels. MolGC calculates the mean absolute error (MAE) of bond lengths by integrating data from various DFT software. It provides interactive and customizable visualization of geometries, enabling users to explore different views for enhanced analysis. In addition, it saves MAE computations for further analysis and offers a comprehensive statistical summary of the results. MolGC effectively addresses complex graph labeling challenges, ensuring accurate identification and categorization of bonds in diverse chemical structures. It achieves a 98.91% average rate in correct bond label assignments on an antibiotics dataset, showcasing its effectiveness for comparing molecular bond lengths across geometries of varying complexity and size. The executable file and software resources for running MolGC can be downloaded from https://github.com/AbimaelGP/MolGC/tree/main .

Surface and interfacial sciences for future technologies

Surface and interfacial sciences for future technologies

Enhanced Surface Determination beyond Photoemission via Auger Photoelectron Coincidence Spectroscopy.

The study of surface properties at the nanoscale plays a crucial role in material science applications. This paper demonstrates the capabilities of Auger PhotoElectron Coincidence Spectroscopy (APECS) to obtain data with varying surface sensitivities from a single measurement. This makes it possible to extract the spectrum from the outermost surface layer even when faced with strongly overlapping surface and bulk spectral features, which we demonstrate by accurately extracting the surface component in Au 4f photoemission. Leveraging high energy resolution, transmission efficiency, tunable photon energy, and remarkable surface sensitivity of the APECS setup, we propose that optimal experimental conditions can be tailored to determine surface spectra accurately for a diverse range of materials. This opens new avenues for advancing our understanding of nanoscale surface phenomena across various material systems.

SnF2-Catalyzed Lithiophilic-Lithiophobic Gradient Interface for High-Rate PEO-based All-Solid-State Batteries.

Polyethylene oxide (PEO)-based all solid-state lithium metal batteries (ASSLMBs) are strongly hindered by the fast dendrite growth at the Li metal/electrolyte interface, especially under large rates. The above issue stems from the suboptimal interfacial chemistry and poor Li+ transport kinetics during cycling. Herein, a SnF2-catalyzed lithiophilic-lithiophobic gradient solid electrolyte interphase (SCG-SEI) of LixSny/LiF-Li2O is in-situ formed. The superior ionic LiF-Li2O rich upper layer (17.1 nm) possesses high interfacial energy and fast Li+ diffusion channels, wherein lithiophilic LixSny alloy layer (8.4 nm) could highly reduce the nucleation overpotential with lower diffusion barrier and promote rapid electron transportation for reversible Li+ plating/stripping. Simultaneously, the insoluble SnF2-coordinated PEO promotes the rapid Li+ ion transport in the bulk phase. As a result, an over 46.7 and 3.5 times improvements for lifespan and critical current density of symmetrical cells are achieved, respectively. Furthermore, LiFePO4-based ASSLMBs deliver a recorded cycling performance at 5 C (over 1000 cycles with a capacity retention of 80.0%). More importantly, impressive electrochemical performances and safety tests with LiNi0.8Mn0.1Co0.1O2 and pouch cell with LiFePO4, even under extreme conditions (i.e., 100 ℃), are also demonstrated, reconfirmed the importance of lithiophilic-lithiophobic gradient interfacial chemistry in the design of high-rate ASSLMBs for safety applications.

Pitfalls and Challenges of Peptide Nucleic Acid Immobilisation on Carbon Surfaces for Sequence-specific Capturing of Nucleic Acid Biomarkers

Nucleic acid sensors based on a peptide nucleic Acid (PNA) probe have seen a surge in interest since their discovery in the 1990s, and after the patent protecting them expired in 2013. The appeal of PNA as capture and/or sensing probes as an alternative to standard DNA or RNA oligonucleotides originates from their superior chemical stability and affinity for complementary oligonucleotides, as well as their increased responsiveness to single base mismatches. The implementation of PNA probes onto optical and electrochemical sensors has showed great promise although progress has been hampered by issues mostly associated with surface chemistry, probe accessibility and non-specific binding. Herein, we report on a systematic comparison between various PNA immobilisation strategies on carbon substrates based on both covalent and non-covalent chemistries. Besides the use of standard electrochemical techniques to characterise the extent of surface modification, the ability of immobilised PNAs to engage in chemical interactions with freely diffusing molecule was also investigated. Using original chemical tags, this study provides a unique insight into the impact of immobilisation chemistries on PNA’s (bio)availability. Rapid immobilisation of biotinylated PNA oligomers on screen-printed carbon electrode (SPCE) coated with adsorbed polystreptavidin (pSA) demonstrated highest efficiency and ease in the preparation process. An original nucleic acid sensor using this immobilisation chemistry is reported that is based on a sandwich assay between a surface bound PNA capture probe and a freely diffusing electrochemically active PNA sensing probe.

Controlling the structure of nitrogen-doped zeolite-templated carbon for CO2 capture based on the synthesis conditions

The surface chemistry and the textural properties of nitrogen-doped zeolite-templated carbon materials (N-ZTC) are decisive for their functionality in CO2 capture. This study analyses how the synthesis conditions affect the structure, formation of N-containing functional groups, thermal stability and CO2 capture of N-ZTC in comparison with nitrogen-free ZTC. Faujasite as a hard template and chemical vapour depositions (CVD) with propene and acetonitrile were used for the synthesis of ZTC and N-ZTC, respectively. XRD, SEM, N2 and CO2 sorption, XPS and TG/DSC analyses showed that the structural ordering and microporous volume in N-ZTC increases with increasing synthesis temperature. Conversely, at higher temperatures, the content of basic pyridinic groups in N-ZTC decreases in favour of stable graphitic nitrogen. The Lewis acid−base interaction of CO2 with the pyridinic groups provides the highest adsorption heats, the highest affinity for CO2 compared to N2 and enhances CO2/N2 selectivity (CO2/N2 selectivities of 127, 95, 89, and 66 for N-ZTC750°C, N-ZTC800°C, N-ZTC850°C and ZTC, respectively). The maximum adsorption capacity was achieved for N-ZTC800°C still yielding a high content of basic groups and a larger micropore volume compared to N-ZTC750°C. The decisive factor for the selectivity is thus the presence of basic centres attainable in N-ZTC at a lower synthesis temperature. The maximum adsorption capacity is associated with a large microporous volume and basic centres in N-ZTC synthesised at medium temperatures. The energy of CO2 adsorption by Lewis acid−base interactions and well-developed micropores are decisive for high selectivity and large adsorption capacity for efficient CO2 capture using N-ZTC materials.