Electron Pair Research Articles

Restructuring surface frustrated Lewis pairs of MgAl-LDH through isomorphous Co doping for accelerating photocatalytic CO2 reduction

The adsorption of carbon dioxide on the catalyst surface is often neglected, and the improvement of adsorption activation capacity is important to realize the efficient conversion of carbon dioxide. In this paper, a novel layered double hydroxide Co-MgAl-LDH (CML) with frustrated Lewis pairs (FLPs) was successfully prepared by one-step hydrothermal doping of transition metal Co, which Co2+ and the oxygen vacancies brought about by the doping (Co2+-Vo) are the Lewis acid site, and adjacent hydroxyls are the Lewis base site, and In-situ experiments and Density Functional Theory (DFT) demonstrated that the FLPs effectively enhanced the CO2 adsorption activation capacity of CML. The present work provides a new idea for modifying Layered double hydroxides (LDH) to construct FLPs, and also offers new hope for constructing high-performance LDH-based CO2 reduction photocatalysts.

Frustrated Al/M Heterobimetallic Complexes (M = Cr, Mo, W) That Exhibit Both Lewis and Radical Pair Behavior.

Exploration of new heterobinuclear Al/M combinations is relevant to contemporary strategies for cooperative bond activation. Here, we report the synthesis and characterization of six new Al/M heterobimetallic complexes (M = Cr, Mo, W) that exhibit end-on "isocarbonyl"-type Al─O═C═M bridges with metalloketene character rather than featuring Al─M─C≡O motifs with metal-metal bonding. The new compounds were characterized experimentally by nuclear magnetic resonance and infrared spectroscopies and theoretically using density functional theory, natural bond orbital, and quantum theory of atoms in molecules calculations. Factors influencing Al─O═C═M vs Al─M─C≡O isomerism were probed both experimentally and computationally. Crossover experiments between different group VI Al/M derivatives and regioselective epoxide ring opening indicate that the Al/M complexes act as masked frustrated Lewis pairs in solution under certain conditions. However, crossover experiments between group VI Al/M complexes and a previously studied Al-Fe complex, as well as computational modeling, imply that the same complexes can also reasonably act as masked frustrated radical pairs (FRPs). FRP reactivity with the group VI Al/M complexes was achieved under photochemical conditions, producing unsaturated metal-carbonyl dimers [(CpCr)2(CO)3]2- and [Mn2(CO)8]2-, which would otherwise be unstable under standard conditions but that are isolable here due to Al(III) coordination. The metal-metal bonding in these unsaturated metal-carbonyl dimers was also analyzed theoretically.

Performance and mechanism of amino-functionalized hydroxyapatite for uranium removal from strong acidity uranium wastewater

The extraction of uranium generates substantial volumes of acidic wastewater loaded with uranium, thereby posing imminent threats to ecological systems and human wellbeing. Consequently, the development of highly effective adsorbent materials for uranium sequestration under strong acidic conditions has become paramount. The amino group contains a lone pair of electrons and is a highly reactive nucleophilic group with a strong affinity for uranium. Herein, we report the amino-functionalized materials (HAP-L-1NH2, HAP-L-2NH2, and HAP-L-3NH2) derived from sodium citrate-modified hydroxyapatite (HAP-L) through a combination of ultrasonic heating and grafting with varying concentrations of 2-amino-1,3-propanediol. The study delved into their performance and underlying mechanisms for uranium removal from acidic wastewater. The findings indicate that an optimal pH of 3.0 favors uranium adsorption for all the materials, with adsorption equilibrium achieved within 30 min. Their respective maximum uranium adsorption capacities stand at 826.44, 990.09, 1060.21, and 884.95 mg g−1, significantly enhancing the adsorptive prowess of amino-functionalized HAP-L materials. The kinetics and thermodynamics manifest that spontaneous endothermic chemisorption occurs on a homogenous monolayer during the adsorption process. Notably, HAP-L-2NH2 robust resilience to interfering ions and exceptional recyclability. After eight cycles of adsorption-desorption, HAP-L-2NH2 retains a uranium adsorption rate of 93.96 % with a stable chemical structure. Application of HAP-L-2NH2 in treating real-world acidic uranium wastewater led to a notable increase in pH from 2.87 to 3.92 and a substantial reduction in uranium concentration from 0.883 mg L−1 to 0.0104 mg L−1. Uranium removal by HAP-L-2NH2 is primarily governed by ion exchange, electrostatic interaction, and co-precipitation reactions.

What Determines the Lewis Acidity of a Bismuthane? Towards Bi-Based FLPs.

Aiming at intramolecular frustrated Lewis pairs (FLPs) based on soft Lewis acidic bismuth centers, a phosphine function was combined with a dichloridobismuthane unit on a phenylene backbone utilizing a scrambling approach. The reaction between two equivalents of BiCl3 and (o-(Ph2P)C6H4)3Bi yielded (o-(Ph2P)C6H4)BiCl2(THF), the structure of which indicated Bi…P interactions and thus a pronounced Lewis acidity at the bismuth center that was confirmed by the Gutmann-Beckett method. However, the system turned out to be insufficient to be utilized for FLP reactivity. Hence, the chloride ligands were exchanged by iodide and C2F5 substituents, respectively. Despite a lower electronegativity the iodide compound exhibits a shorter Bi…P contact, while the C2F5 substituents led to a further decrease of the Lewis acidity, despite their high group electronegativity. DFT calculations rationalized this by a quenching of the Lewis acidity inherent to the σ*(Bi-C) orbital by negative hyperconjugation from occupied p-orbitals at the F atoms. Furthermore, it turned out that the strength of the covalent Bi-X σ-bond is a more important factor than the charge at Bi in determining the energetic accessibility and thus Lewis acidity of the antibonding σ*(Bi-C) orbital.

First copper (II) oxo-selenite-sulfate Cu4O(SeO3)(SO4)2 and the role of a lone electron pair in open framework crystal structure formation

New copper oxo-selenite-sulfate Cu4O(SeO3)(SO4)2 was prepared by the reaction of anhydrous CuSO4, CuO, and SeO2 in a sealed silica tube. The compound crystallizes in the triclinic P1‾ space group, with cell parameters a = 8.379(3)Å, b = 8.402(4) Å, c = 8.497(3) Å, α = 82.988(14) °, β = 61.006(9) °, γ = 62.105(14)°. The selenite-sulfate features open-framework crystal structure with two types of channels, where lone electron pairs of SeO32− groups are located. DFT calculations were made to support this statement and to investigate the nature of chemical bonding in the crystal structure and estimate the band gap (3.3 eV).The crystal structure of Cu4O(SeO3)(SO4)2 was compared to the related triclinic form of Cu4O(SeO3)3. The role of sulfate groups is also discussed.

Dative Bonding in Quasimetallatranes Containing Group 15 Donors (Y = N, P, and As) and Group 14 Acceptors (M = Si, Ge, Sn, and Pb).

Metallatranes and their analogous fused ring [3.3.0] bicyclic compounds, quasimetallatranes, have emerged as fascinating molecular systems with intriguing structural, bonding, and conformational properties. We present a comprehensive investigation aimed at unraveling the nature of dative bonding and exploring the conformational flexibility of these compounds. We extensively characterize the dative bond between the metal center and the electron pair donor, using a range of modeling techniques. Our analyses involve structural optimizations, molecular orbital examinations, and covalency ratio calculations, which provide a thorough understanding of the bonding interactions responsible for the stability of these systems. The results confirmed the presence of dative bonds, supported by the close proximity between the metal and the electron-donating group, and the observation of overlapping electron density. Our studies reveal a correlation between the size of the electron-donor and the coordinating metal atom, and the strength of the dative interaction, as indicated by the bond length and the Wiberg bond indices. This bond strength, in turn, influences the conformational preferences adopted by these compounds. This investigation sheds light on the fundamental aspects of the fused ring [3.3.0] bicyclic quasimetallatrane compounds and offers valuable insights into their unique properties.

A DFT Mechanistic Study on the Aza-Aldol Reaction of Boron Aza-Enolates: Relative Stability of Six-Membered Transition State and Its Relevance to the Coordination Mode of the Leaving Group.

The mechanism of the aza-aldol reaction between boron aza-enolate and benzaldehyde is investigated by using density functional theory calculations. The result shows that the syn-E isomer is preferentially formed, consistent with experimental observations. The six-membered ring transition state (TS) with the boat form leads to the E isomer, while the more unstable chair TS does to the Z isomer. The preference of the syn isomer is determined by the interactions between the substituents of aza-enolate and benzaldehyde. Structural distortion and intrinsic reaction coordinate analyses of simplified model systems provide insights into the origin of the relative stability of the rate-determining TS with boat and chair forms. The boat TS is an early TS; thus, minimal structural distortions of the reactant are required to reach this TS. The Lewis pair interactions between the boron and imine groups during B-N elimination also influenced the relative stability of the TSs. This interaction involves the nitrogen lone pair in the boat TS, while the π(N═C) orbital is involved in the chair TS. The Lewis pair with the lone pair stabilizes the TS more than that with the π orbital. The boron aza-enolate with 9-BBN generates an ate complex and forms C-C bonds sequentially, whereas that with Bpin does not generate an ate complex and exhibits the concerted formation of B-O and C-C bonds. Thus, the higher electrophilicity of boron such as 9-BBN enhances the reactivity by facilitating the formation of the ate complex. A reaction design is proposed to reverse the syn/anti selectivity. Proof-of-concept DFT calculations suggested that the modification of the imine group would change the relative stability of the boat/chair TSs and give the anti-product.

Construction of C3N4/Ag2S p-n semiconductor heterojunction coupled with Ag-induced SPR effect on CF cloth for improving photocatalytic activity

C3N4/Ag2S p-n semiconductor heterojunction coupled with Ag-induced SPR effect on carbon fiber cloth with large macroscopic area, recyclability and excellent photocatalytic performance was prepared by thermal condensation-chemical precipitation. CF/C3N4/Ag/Ag2S cloth showed strong Vis-NIR light absorption and outstanding separation efficiency of photo-generated electron and hole pairs. CF/C3N4/Ag/Ag2S cloth displayed a markedly enhanced catalytic activity (94 % of TC, 85 % of Cr(VI)) compared with CF/C3N4 cloth (52 % of TC, 50 % of Cr(VI)) or CF/Ag/Ag2S cloth (34 % of TC, 19 % of Cr(VI)), attributing to the establishment of p-n junction along with Ag SPR effect. Moreover, degradation pathways for TC were proposed utilizing HPLC-MS and Fukui index analysis, and photocatalytic mechanism was confirmed by active species experiments and DFT computations. This facile strategy provides novel approach to the synthesis of material with large macroscopic areas, recyclability, and excellent photocatalytic property for degrading contaminants from wastewater.

The Role of Frustrated Lewis Pair in Catalytic Transfer Hydrogenation of Furfural using Nickel Single-Atom Catalysts: A Theoretical Study.

The burgeoning field of frustrated Lewis pair (FLP) heterogeneous catalysts has garnered significant interest in recent years, primarily due to their inherent ability to activate H-source molecules, such as H2, thereby facilitating hydrogenation reactions. However, the application of single metal atom catalysts incorporating FLP sites has been relatively under-explored. In this study, non-precious transition metal atoms were anchored onto a C2N framework with an intrinsic cavity and a defective N-C sheet. Theoretical calculations substantiated energy barriers as low as 0.10 eV for isopropanol activation, thereby positioning these catalysts as highly promising candidates for catalytic transfer hydrogenation of furfural. Electronic structure analyses revealed that the H-O bond breakage in isopropanol molecules was significantly facilitated by the presence of FLP sites within the catalysts. Notably, both Ni-C2N and Ni-N6-C demonstrated exceptional potential as selective catalysts for the hydrogenation of furfural into furfuryl alcohol, exhibiting remarkably low barriers of only 0.65-0.72 eV for the rate-determining steps, which are notably lower than those observed in many traditional catalysts. Theoretical investigations strongly imply that the construction of single atom catalysts with FLP sites could significantly enhance the activity and selectivity for hydrogenation reactions, thus stimulating the experimental synthesis of such catalysts.

Highly Tolerant Living/Controlled Anionic Polymerization of Dialkyl Acrylamides Enabled by Zinc Triflate/Phosphine Lewis Pair.

Living polymerizations of polar vinyl monomers have been successful for decades. However, they still suffer the following challenges: fast propagation, air-moisture tolerance, and negligible side reactions even at elevated temperatures. Here, we developed an unprecedented polymerization that overcomes these limitations using a Lewis pair catalyst. The anionic polymerization of dialkyl acrylamides proceeded in a living/controlled matter using Zn(OTf)2/PPh3 within a wide temperature range of 25-100 °C for short times (1-10 min) even under open-air conditions. The recovery and reuse of Zn(OTf)2 without loss of polymerization activity were observed to be possible. The polymerization was retarded by excess Zn(OTf)2, the additive methanol, and water, indicating equilibriums of the propagating species with them. The putative propagating zinc triflate-ate complex was tolerant to the protic additives and significantly selective for the propagation.

Construction of heterogeneous frustrated lewis pairs based on covalent organic frameworks stabilized boron cations and investigation of cycloaddition reaction performance

Frustrated Lewis Pairs (FLPs) catalysts have been widely designed and synthesized in current chemistry, with the key being the selection of boron-based Lewis acids. Among novel boron-based Lewis acids, boron cations with higher Lewis acidity caused by cationic charge have been proven to have special reactivity. However, the current boron cations have only been used to construct homogeneous FLPs, which would be difficult to meet the industrial process demand for FLPs catalysts, possibly due to the lack of suitable stabilizers. In this paper, we propose a strategy to construct heterogeneous FLPs using covalent organic frameworks (COFs) stabilized boron cations as Lewis acid. Firstly, heterogeneous Lewis acid COFs@[B(C6F5)2]+[Al2Cl7]- was prepared by stabilizing boron cations with CN bonds in COFs, followed by introducing tBu3P to construct heterogeneous FLPs COFs@[B(C6F5)2]+[Al2Cl7]-/tBu3P. Meanwhile, these FLPs catalysts exhibited excellent catalytic and cyclic performance in the preparation of cyclic carbonates by CO2 addition from epoxy compounds.

Preparation of Guanidine-Grafted NH2-MIL-101(Fe)/Polyvinylidene Fluoride Mixed Matrix Membranes for Adsorption of Pb2+ for Isopropanol Purification.

Electronic-grade isopropyl alcohol is widely utilized in the cleaning of semiconductors and microelectronic components. Removing ions like Pb2+ is crucial since the presence of impurities may cause degradation of electronics, increased failure rates, and short circuits. Membrane materials offer a number of advantages in the field of adsorption separation; however, the lack of adsorption sites results in limited adsorption capacity. In the current work, guanidino-grafted NH2-MIL-101(Fe) was incorporated into polyvinylidene fluoride (PVDF) to prepare MOF/PVDF mixed matrix membranes (NM/PVDF) for the removal of Pb2+ from isopropanol. Benefiting from the larger specific surface area and more lone electron pairs in the guanidine group, the Pb2+ adsorption capacity of the as-prepared NM/PVDF membrane was 29.4458 mg/g, which was higher than that of the NH2-MIL-101(Fe)/PVDF membrane (20.9306 mg/g) and the pure PVDF membrane (6.7324 mg/g). The NM/PVDF membrane was able to reduce the concentration of Pb2+ from 500 to 86.73 ppb. This work highlights the potential of guanidine-grafted Fe-based MOFs/PVDF membranes as adsorbents for acquisition of electronic-grade solvents.

AIM/NBO Analysis of the Geminal Coupling Constants in the Stabilization of A-Type Dimeric Proanthocyanidin: Angular Dependence.

The angular dependence of the indirect short-range spin-spin coupling constants (SSCC), the geminal , , and in A-type dimeric proanthocyanidin, was investigated using density functional theory. We studied the rotation of ring B around the bond. Therefore, we calculated hyperconjugative charge transfers and bond polarizations within the natural bond orbital (NBO) approach, performing a topological study based on Bader's theory, AIM (atoms in molecules), and analyzing the angular dependence of AIM/NBO parameters. The results describe a relationship between the geminal coupling that changes with angular variation and NBO charge transfers to the bonds involved in the coupling pathways that can explain the behavior of the former property. Based on AIM/NBO data, inductive and mesomeric effects were described and quantified, showing a clear correlation with the stabilization of the structure, demonstrating a resonance-assisted inductive effect. We also set out strong hyperconjugative interactions (anomeric effect) involving nonbonding electron pairs of oxygen atoms. This analysis of coupling constants supports previous models by other authors and shows the application in this particular case. Moreover, the SSCCs studied herein are used for identifying stable structures and conformational search analysis of flavonoids. Finally, our results show the relationship between SSCCs and the structure stabilization and charge delocalization effects.

The role of linkers and frustrated lewis pairs catalysts in the formation of zwitterionic 1,2-anti-addition product with non-conjugated terminal diacetylenes: A computational study

This study presents a computational investigation into the mechanistic pathway and the linker units involved in forming the zwitterionic 1,2-anti-addition product of non-conjugated diacetylenes, di(propargyl)ether (DPE), di(prop-2yn-1yl)sulfane (DPS) and 1,6-Heptadiyne (HD) catalyzed by the inter-molecular phosphine/borane frustrated Lewis pairs (FLPs), i.e., PPh2[C6H3(CF3)2](P-CF)/[B(C6F5)3]([B]) and P(o-tolyl)3(P-tol)/[B(C6F5)3]([B]). The potential energy surface (PES) calculations reveal that the anti-addition of P-CF to the internal C-atoms of acetylene units is energetically more favored than that of the addition of P-tol in DPE, DPS, and HD by ∼10.0, ∼9.2, and ∼6.0 kcal/mol, respectively. The calculations performed with DPE contain “—O—,” linker unit exhibits superior reactivity than DPS and HD, which suggests the electronegativity of linkers plays a significant role and facilitates the addition of Lewis bases. The higher electronegativity of linker units enables the 1,2-addition reaction by lowering the free energy activation barriers, as observed in the DFT calculations. The Molecular Electrostatic Potential (MESP) study shows that the electrostatic interactions favor the addition of P-CF to the active acetylene positions (C5/C4/C4) of [B]-DPE/DPS/HD-π complexes than the P-tol. The Distortion/Interaction (D/I) analysis reveals that transition states involving P-CF (TS1, TS3, and TS5) exhibit more interaction energy (ΔEInt) and less distortion energies (ΔEd) than that of the P-tol (TS2, TS4, and TS6). Further, the Energy Decomposition Analysis (EDA) also rationalizes the preferential approach of the electron-deficient Lewis base over the electron-rich one on the basis of the significant contribution of orbital interaction energies (ΔEorbital) in the cases of P-CF; TS1, TS3, and TS5. This study suggests that the electronic effects of substrates and the FLPs are crucial to facilitate the desired products formed with non-conjugated terminal alkynes.

Selective Reduction of Nitroolefins to Nitroalkanes Using Frustrated Lewis Pairs Modified NU-1000 MOF

Selective Reduction of Nitroolefins to Nitroalkanes Using Frustrated Lewis Pairs Modified NU-1000 MOF

A Novel Trifunctional Catalyst Enables Radical–Radical Coupling via Intramolecular Frustrated Lewis Pairs

A Novel Trifunctional Catalyst Enables Radical–Radical Coupling via Intramolecular Frustrated Lewis Pairs

On the Structure of Tl2Pb(SO4)2 and Crystal Chemistry of Thallium‐Containing Sulfates

AbstractSingle crystal of a thallium‐containing sulfate Tl2Pb(SO4)2 was prepared through hydrothermal crystallization starting from Tl2CO3, Pb(NO3)2 and H2SO4. The crystal structure was solved from single‐crystal X‐ray diffraction data: Tl2Pb(SO4)2 crystallizes in space group R m with lattice parameters of a=5.5955(2) Å, c=22.1001(9) Å, and Z=3, which is also corroborated by Rietveld refinement on X‐ray powder data. The crystal structure can be regarded as [Pb(SO4)2]2− sheets intercalated by double layers of Tl+ along the c‐axis. From a mineralogical perspective, Tl2Pb(SO4)2 belongs to the palmierite family and can further be classified within palmierite‐supergroup. Validation of the structure models was carried out utilizing various concepts including Bond Valence (BV), Charge Distribution (CD) and Madelung Part of Lattice Energy (MAPLE). Notably, a contrast in stereochemical activity of 6s2 lone electron pair (LEP) between Tl+ and Pb2+ is interpreted in terms of bonding behaviours as well as Wang‐Liebau Eccentricity (WLE) parameters. Moreover, an extensive investigation into the crystal chemistry of thallium‐containing sulfates was conducted for the first time, focusing on the coordination environment and bonding behaviour of Tl+ and corresponding WLE parameters. A comparative analysis of these structurally related compounds including Tl2Pb(SO4)2, Tl3H(SO4)2, TlBi(SO4)2, TlIn(SO4)2, TlRh(SO4)2, and TlAl(SO4)2 was delineated.

MoS2 coupled with ball milling co-modified sludge biochar to efficiently activate peroxymonosulfate for neonicotinoids degradation: Dominant roles of SO4•-, 1O2 and surface-bound radicals

An efficient catalyst of molybdenum disulfide (MoS2) coupled with ball milling modified sludge biochar (BMSBC) was prepared to efficiently activate peroxymonosulfate (PMS) for neonicotinoids elimination. As expected, 95.1% of imidacloprid (IMI) was degraded by PMS/BMSBC system within 60 min and it was accompanied by the outstanding mineralization rate of 71.9%. The superior pore structures, rich defects, oxygen-containing functional groups and grafted MoS2 on BMSBC offered excellent activation performance for PMS. The influencing factor experiments demonstrated that PMS/BMSBC system performed high anti-interference to wide pH range and background constituents (e.g., inorganic ions and humic acid). Quenching experiments and electron paramagnetic resonance analysis revealed that SO4•−, 1O2, and surface-bound radicals played critical roles in IMI degradation. Electron donors on biochar activated PMS, producing surface radicals. The lone pair electrons within the Lewis basic site of C=O on BMSBC enhanced PMS decomposition by facilitating the cleavage of the -O-O- bond in PMS to release 1O2. The activation process of PMS by MoS2 accelerated the oxidation of Mo (IV) to Mo (VI) to generate SO4•−. Based on the transformed products (TPs), four degradation pathways of IMI in PMS/BMSBC system were suggested, and all TPs toxicity levels were lower than that of IMI by ECOSAR analysis. Additionally, BMSBC exhibited outstanding sustainable catalytic activity towards PMS activation with the well accepted degradation rate of 71.3% for IMI even after five reuse cycles. PMS/BMSBC system also exhibited satisfactory degradation rates (>71.8%) for IMI in various real waters (e.g., sewage effluent and livestock wastewater). Furthermore, PMS/BMSBC system also offered a favorable broad-spectrum elimination performance for other typical neonicotinoids (e.g., thiamethoxam, clothianidin, thiacloprid) with the degradation rates over 98%. This study has developed a desirable neonicotinoids purification technology in view of its high degradation/mineralization rate, outstanding detoxification performance, satisfied anti-interference to ambient conditions and sustainable sludge management.

Unraveling Lewis acid-base sites in defected MOFs for catalyzing dicyclopentadiene hydrogenation via a DFT study and descriptor exploration

The 12-connected UiO-66 MOFs with great defect regulation ability have attracted significant attention due to the easily tunable electronic structure and surface electrostatic potential distribution of metal nodes. In this density functional theory (DFT) study, we systematically explored the effect of bi-active site types as the frustrated Lewis pair (FLP) and classical Lewis pair (LP) as well as metal elements of secondary building units (SBUs) on the catalytic hydrogenation of dicyclopentadiene (DCPD) to tetrahydrodicyclopentadiene (THDCPD). These design strategies effectively modulate the frontier molecular orbital energy level that determines the binding strength between MOFs and adsorbed species *Hδ+-Hδ- and charges transfer before and after H2 chemisorption. We also found that the heterolytic H2 adsorption energy and charges transfer linearly correlate with the energy barrier. In order to unravel the clear-cut designing strategies and further simplify computational complexity, we firstly proposed the ADCH charges difference between the Lewis acid and the Lewis base centers (ΔQM-O) as an intrinsic descriptor for catalytic activity of DCPD into THDCPD, which can effectively describe the reactivity and electrostatic effects of oppositely charged bi-active sites in the system. Furthermore, the defective UiO-66(Ce) MOF with moderate ΔQM-O effectively balance the contradiction between the barriers of two primitive reaction: the heterolytically H2 dissociation to *Hδ+-*Hδ- and the desorption of the active hydrogen species to hydrogenate 8,9-dihydrodicyclopentadiene (8,9-DHDCPD), resulting in the optimal catalytic performance. This work provides a deep understanding of the catalytic mechanism of MOFs with multiple active sites and might open up avenues for the rational design of novel hydrogenation catalysts.

Realization of hydrogenation-induced superconductivity in two-dimensional Ti2N MXene.

Two-dimensional (2D) MXene superconductors have been currently attracting considerable interest due to their unique electronic properties and diverse applicability. Utilizing first-principles computational methods, we have designed two distinct configurations of hydrogenated 2D Ti2N MXene materials, namely Ti2NH2 and Ti2NH4, and have conducted an exhaustive analysis of their structural stability, electronic characteristics, and superconductivity. Hydrogenation endows monolayer Ti2N with inherent metallic characteristics, as evidenced by an elevated density of states (DOS) at the Fermi level (Ef). Notably, Ti2NH4 exhibits a superconducting critical temperature (Tc) of 15.8 K, which is predominantly ascribed to the electronic contributions stemming from the Ti 3d orbitals. Analysis of phonon dispersion underscores the pivotal role that diverse lattice vibrational modes play in electron-phonon coupling (EPC), particularly the significance of low-frequency vibrations for facilitating electron pairing and the emergence of superconductivity. Furthermore, strain engineering can effectively modulate the superconducting properties of Ti2NH4, with a 2% tensile strain enhancing the EPC strength (λ) to 0.857 and increasing Tc to 18.7 K. This research elucidates the superconducting mechanisms of hydrogenated Ti2N structures, offering valuable insights for the development of novel 2D superconducting materials.