Strong Orbital Interactions Research Articles

Synthesis, structure, DFT study and molecular docking inspection of spirobi[hexahydropyrimidine]-diones derivative

It has been established that three-component condensation of benzaldehyde, acetone and urea catalyzed H2SO4 leads to the formation of spirobi[hexahidropyrimidine]-dione derivatives. The structure of the synthesized compound has been proved by X-ray method. The results of the quantum theory of atom-in-molecule and noncovalent interaction index analysis showed no intramolecular hydrogen bonds in the molecule studied. However, it contains four N-H bonds and two C=O groups. Based on the result of the DFT-NBO analysis, it was the lone pairs of oxygen on the C=O group which are forming strong orbital interactions with the antibonding orbital of the C-N single bond. The molecular docking was performed to investigate potential binding interactions of the compound with four target proteins including 5I4T (HIV-1), 5R7Z, 6M71 and 6VYB (SARS-Cov-2). Additionally, in-silico drug-likeness and ADME studies suggested oral activity (violations ≤ 1) of scaffold and predicted to be actively effluxed by P-gp (PGP+).

Exploring structural basis of photovoltaic dye materials to tune power conversion efficiencies: A DFT and ML analysis of Violanthrone

This study employs a systematic approach to modify Violanthrone (V) structures and analyze their impact on photovoltaic (PV) properties. We use cheminformatics based Python library based RDKit tool to calculate their structural descriptors for to correlate them with their PV parameters. Our analysis reveals a positive correlation for their Open-Circuit Voltage (Voc) and Fill Factor (FF) for indicating that their higher voltage output is associated for their efficient charge carrier mobilities. We also predict their Power Conversion Efficiency (PCE) by drawing their their Scharber diagram which achieves their promising efficiency of up to 15 %. To further enhance the reliability our work, we conduct an extensive literature survey of such organic materials to predict their PCEs by their Machine Learning (ML) after utilizing various ML models. Among five tested ML models, it identifies the Random Forecast (RF) model and Gradient Boosting (GB) models as as the optimal one (R-squared value: 0.82). Their feature importance reveals that their FF is the most significant feature to impact their PCEs (importance value: 10.9). Furthermore, we observe a negative correlation between orbital interaction strength (E(2)) values and orbital energy differences E(j)-E(i) which indicates that their stronger orbital interactions are associated with their smaller energy differences. Our study provides valuable insights for their structural basis to PV material designs for enabling their design for efficient materials in energy conversion.

Enhanced hydrogen storage of single-layer blue phosphorus by synergistic effect between doped lightweight elements and grafted lithium atoms

Single-layer blue phosphorus (SLBP) has displayed charming photoelectric performances, but its property in hydrogen storage is not outstanding due to the weak interactions. To expand the application of SLBP in hydrogen storage, we attempt to screen SLBP-based materials with stable structures and strong polarity using density functional theory by doping lightweight elements and grafting alkali metal atoms. The simulation results indicate that the lightweight elements (B, C, N, O and F) doped SLBP systems have more stable structures due to the strong orbital interaction than pure SLBP, and exhibit electron deficient characteristics. Compared to the pure SLBP, the H2 adsorption energies of the doped systems improve and range from 0.05 to 0.09 eV, but it still cannot meet the requirements of ideal hydrogen storage. Therefore, the lightweight element doped SLBP systems are further grafted by Li atom. Under the synergistic effect of doping lightweight elements and grafting Li atoms, H2 molecules are strongly polarized, and the corresponding adsorption energies of H2 reach to 0.16, 0.26, 0.28, 0.30, and 0.10 eV, respectively. It is worth emphasizing in the C-doped SLBP system that the hydrogen storage capacity of reaches 5.53 wt% for each Li atom adsorbs one hydrogen molecule and the corresponding adsorption energy is 0.23 eV/H2 when the ratio of C to P atoms increases to 6:26. For each Li atom adsorbs two hydrogen molecules in the same hydrogen storage system, the hydrogen storage capacity reaches 10.48 wt% with 0.18 eV/H2 adsorption energy. We hope these results can provide theoretical basis and scientific guidance for searching for SLBP-based materials with excellent hydrogen storage performances at ambient temperature.

Precisely constructing orbital coupling-modulated iron dinuclear site for enhanced catalytic ozonation performance

The advancement of atomically precise dinuclear heterogeneous catalysts holds great potential in achieving efficient catalytic ozonation performance and contributes to the understanding of synergy mechanisms during reaction conditions. Herein, we demonstrate a "ship-in-a-bottle and pyrolysis" strategy that utilizes Fe2(CO)9 dinuclear-cluster to precisely construct Fe2 site, consisting of two Fe1-N3 units connected by Fe-Fe bonds and firmly bonded to N-doped carbon. Systematic characterizations and theoretical modeling reveal that the Fe-Fe coordination motif markedly reduced the devotion of the antibonding state in the Fe-O bond because of the strong orbital coupling interaction of dual Fe d-d orbitals. This facilitates O-O covalent bond cleavage of O3 and enhances binding strength with reaction intermediates (atomic oxygen species; *O and *OO), thus boosting catalytic ozonation performance. As a result, Fe dinuclear site catalyst exhibits 100% ozonation efficiency for CH3SH elimination, outperforming commercial MnO2 catalysts by 1,200-fold. This research provides insights into the atomic-level structure-activity relationship of ozonation catalysts and extends the use of dinuclear catalysts in catalytic ozonation and beyond.

Rational Design of Metallylenes for Hydrogenation Reactions

AbstractThe hydrogenation of alkenes, alkynes, carbonyls, and imines by H2‐activated metallylenes (H3C−EH2−L, CELH2; E=Si, Ge, Sn and L=NMe2, PMe2) was studied using relativistic density functional theory at ZORA‐BP86/TZ2P. By means of activation strain and Kohn–Sham molecular orbital analyses, the physical factors underlying the trends in reactivity were identified and quantified. Firstly, the hydrogenation reactivity increases on descending Group 14, that is from silylenes (E=Si) to stannylenes (E=Sn). This reactivity trend originates primarily from a reduced energy required to break the bonds between the Group 14 atom and the hydrogen atoms because the strength of these bonds decreases from Si−H to Ge−H to Sn−H. Secondly, the reactivity decreases as the Group 15 ligand changes from nitrogen to phosphorus (L=NMe2, PMe2) which stems from the trigonal pyramidal PMe2 geometry compared to the trigonal planar NMe2 geometry. The latter can, therefore, effectively engage in stronger orbital interactions with the substrate than the former, due to a more efficient HOMO–LUMO orbital overlap. By combining our insights, we rationally designed an optimally tuned catalyst (Group 14 atom and ligand) considering the overall catalytic cycle involving H2 activation of the metallylene and subsequent hydrogenation.

Enhanced Al‐Storage Performance by Electronic Properties Optimization and Structural Customization in MOF‐Derived Heterostructure

AbstractChalcogenide cathodes with multi‐electron transfer characteristics are indispensable to aluminum‐ion batteries (AIBs). Nevertheless, their grievous capacity degradation and sluggish reaction kinetics remain fundamental challenges for the practical application. Herein, a Cu2S/Ni3S2 multiphase structure within the metal‐organic frame (MOF) derived carbon decoration layer (CNS@MC) is constructed to elevate the intrinsic electronic properties of chalcogenide cathode and realize high‐performance AIBs. The existence of outer carbon layer and strong orbital interaction at inner heterointerfaces eliminates the bandgap and arises more electrons at Fermi level, efficiently reducing the energy barrier for electron transfer and achieving high reactivity within cathodes. The CNS@MC also presents a strong electronic interaction with active solvent groups, which is beneficial to capture Al3+ and facilitate the three‐electron charge‐storage reactions. Experimental results demonstrate that the tailored CNS@MC cathode possesses superior redox kinetics due to the sufficient surface area and rapid Al‐ion diffusion during cycling. Meanwhile, the robust CNS@MC delivers ultra‐high electrochemical stability (131.1 mAh g−1 over 3500 cycles) with high coulombic efficiency and outstanding rate performance. This work offers new opportunities for optimizing the intrinsic properties of the chalcogenide electrodes based on MOF derivatives and heterostructure, providing novel thoughts for designing high‐performance AIBs.

Unveiling a unique outer-sphere pathway in manganese-catalyzed acceptorless dehydrogenation reaction.

First-row transition metals are widely used in acceptorless dehydrogenative coupling reactions, making the detailed investigation of their catalytic mechanisms crucial for the rational design of efficient catalysts. In this study, density functional theory (DFT) was employed to explore the mechanism of an acceptorless dehydrogenation reaction catalyzed by a bifunctional complex based on a high-spin Mn(II) center. The computational results reveal that the Mn(II) catalyst follows a novel dehydrogenation pathway, where the external base KOH first coordinates to the metal center, and dehydrogenation proceeds via an outer-sphere mechanism. The hydride transfer step is identified as the rate-determining step, with an energy barrier of 26.3 kcal mol-1, consistent with experimental results. To further investigate the selectivity of the mechanism, energy decomposition analysis (EDA) and extended transition state-natural orbitals for chemical valence (ETS-NOCV) analysis were conducted on key transition states. The results show that the small steric hindrance and strong orbital interactions of the external base KOH are the key factors contributing to the selectivity of this mechanism. These findings not only deepen our understanding of the reaction mechanism but also provide valuable theoretical insights for the design and optimization of future acceptorless dehydrogenation catalysts.

Investigation of the Effect of Solvents on the Synthesis of Aza-flavanone from Aminochalcone Facilitated by Halogen Bonding.

It has been recognized that CBr4 can give rise to a noncovalent interaction known as halogen bond (XB). CBr4 was found to catalyze, in terms of XB formation, the transformation of 2'-aminochalcone to aza-flavanone through an intramolecular Michael addition reaction. The impact of XB and the resulting yield of aza-flavanone exhibited a pronounced dependence on the characteristics of the solvent. Notably, yields of 88% in ethanol and 33% in DMSO were achieved, while merely a trace amount of the product was detected in benzene. In this work, we use a computational modeling study to understand this variance in yield. The reaction is modeled at the level of density functional theory (based on the M06-2X exchange-correlation functional) with all-electron basis sets of triple-ζ quality. Grimme's dispersion correction is incorporated to account for the noncovalent interactions accurately. Harmonic frequency calculations are carried out to establish the character of the optimized structures (minimum or saddle point). Our calculations confirm the formation of an XB between CBr4 and the reacting species and its role in lowering the activation energy barrier. Stronger orbital interactions and significant lowering of the steric repulsion were found to be important in lowering the activation barrier. The negligible yield in the nonpolar solvent benzene may be attributed to the high activation energy as well as the inadequate stabilization of the zwitterionic intermediate. In ethanol, a protic solvent, additional H-bonding contributes to further lowering of the activation barrier and better stabilization of the zwitterionic intermediate. The combined effects of solvent polarity, XB, and H-bond are likely to give rise to an excellent yield of aza-flavanone in ethanol.

Modulating the d-Band Center Enables Ultrafine Pt3 Fe Alloy Nanoparticles for pH-Universal Hydrogen Evolution Reaction.

By providing dual active sites to synergistically accelerate H2 O dissociation and H+ reduction, ordered intermetallic alloys usually show extraordinary performance for pH-universal hydrogen evolution reaction (HER). Herein, activated N-doped mesoporous carbon spheres supported intermetallic Pt3 Fe alloys (Pt3 Fe/NMCS-A), as a highly-efficient electrocatalyst for pH-universal HER, are reported. The Pt3 Fe/NMCS-A exhibits low overpotentials (η10 ) of 13, 29, and 48mV to deliver 10mAcm-2 in 0.5mH2 SO4 , 1.0mKOH, and 1.0m phosphate buffered solution (PBS), respectively, as well as robust stability to maintain the overall catalytic performances. Theoretical studies reveal that the strong Pt 5d-Fe 3d orbital electronic interactions negatively shift the d-band center (εd ) of Pt 5d orbital, resulting in reduced H* adsorption energy of Pt sites and enhanced acidic HER activity. With Pt and Fe acting as co-adsorption sites for H* and *OH intermediates, respectively, a low energy barrier is required for Pt3 Fe/NMCS-A to dissociate H2 O to afford H* intermediates, which greatly promotes the H* adsorption and H2 formation in alkaline and neutral conditions. The synthetic strategy is further extended to the synthesis of Pt3 Co and Pt3 Ni alloys with excellent HER activity in pH-universal electrolytes, demonstrating the great potential of these Pt-based alloys for practical applications.

From tetramerization to oligomerization/polymerization of ethylene by dinuclear pyridyl‐imine Co‐ and Ni‐based catalysts

A series of dinuclear pyridyl‐imine Co‐ and Ni‐based complexes (Co: C1 and C2 and Ni: C3 and C4) were prepared in reasonable yields through one‐pot synthesis method. Toward ethylene oligomerization/polymerization, C1 and C2, activated by MMAO, were capable to produce oligomers with moderate activity (up to 5.1 × 105 g mol−1 Co h−1 for C2) which α‐C8 was the major product. In contrast, C3 and C4 polymerized ethylene that the activity of C4 was twofold greater than C2. The high impact of o‐substituent in C2 and C4 was along with dinuclearity effect leading to high productivity and selectivity for ethylene oligomerization and polymerization, respectively. Moreover, polymerization parameters had strong influence on catalytic behavior of C4 and polyethylene samples made. For instance, high sensitivity of the structures led to formation of an oily branched oligoethylene to highly branched, high Mw polyethylene by changing the polymerization conditions. Polymerization of higher α‐olefins such as 1‐hexene and 1‐octene, moreover, emphasized the effect of effective distance between the centers where an oily low Mw oligo‐1‐hexene and a solid poly(1‐octene) having higher Mw were yielded. On the other side, quantum chemistry calculations were performed to investigate the structural properties and reactivity of the Ni‐ and Co‐based species. The obtained results indicated that the Ni atoms have strong molecular orbital interactions with the CC bond which may increase the reactivity of the catalyst in comparison with the Co metals.

Carcinogenic dioxane detection using pristine and metal-doped 2D VSe2: Insights from density functional theory simulations

Dioxane (diethylene oxide) is a synthetic organic compound classified as heterocyclic ether, a potentially carcinogenic water toxicant. Prolonged exposure can cause eye irritation, carcinogenic liver reactions, and other severe issues. Therefore, efficient dioxane detectors are needed to be designed and developed. Inspired by the recent developments of 2D materials in biosensing, in this work, the dioxane detection potentiality of pristine and metal-doped (Al, Au, and Ag) 2D VSe2 have been systematically examined using Density Functional Theory (DFT) based simulations. Among all the metallic dopants considered, Al binds energetically on the VSe2 surface with an energy of −2.158 eV. The adsorption of dioxane was studied by considering the electronic properties, adsorption energy, orbital interactions, and charge transfer. Our DFT calculation suggests that dioxane adsorption in Al-doped VSe2 is more promising than the pristine and other metal-doped VSe2 systems, due to the reasonable adsorption energy of −0.80 eV, charge transfer of −0.567e, and strong orbital interaction between Al 3p and O 2p orbitals. Additionally, the room temperature structural solidity of the sensor has also been verified using the ab initio molecular dynamics simulations. The reported theoretical results inspire the fabrication and engineering of efficient dioxane sensors using Al-doped VSe2.

Electrochemically stable frustrated Lewis pairs on dual-metal hydroxides for electrocatalytic CO2 reduction.

The sluggish kinetics of CO2 activation and reduction severely limit the energy conversion efficiency of electrocatalytic CO2 reduction into fuels. Here, ZnSn(OH)6 with an alternating arrangement of Zn(OH)6 and Sn(OH)6 octahedral units and SrSn(OH)6 with an alternating arrangement of SrO6 and Sn(OH)6 octahedral units were adopted to check the effects of frustrated Lewis pairs (FLPs) on electrochemical CO2 reduction. The FLPs were in situ electrochemically reconstructed on ZnSn(OH)6 by reducing the electrochemically unstable Sn-OH to Sn-oxygen vacancies (Sn-OVs) as a Lewis acid site, which are able to create strong interactions with the adjacent electrochemically stable Zn-OH, a Lewis base site. Compared to SrSn(OH)6 without FLPs, the higher formate selectivity of ZnSn(OH)6 originates from the strong ability of FLPs to capture protons and activate CO2via the electrostatic field of FLPs triggering better electron transfer and strong orbital interactions under negative potentials. Our findings may guide the design of electrocatalysts for CO2 reduction with high catalytic performances.

Orbital Interactions between the Organic Semiconductor Spacer and the Inorganic Layer in Dion-Jacobson Perovskites Enable Efficient Solar Cells.

2D Dion-Jacobson (DJ) perovskites have become emerging photovoltaic materials owing to their intrinsic structure stability. However, as insulating aliphatic cations are widely used as spacers, the interactions between the spacers and inorganic layers in DJ perovskites have rarely been studied. Here, an organic semiconductor spacer with two covalently connected thiophene rings, namely bithiophene dimethylammonium (BThDMA), is successfully developed for 2D DJ perovskite solar cells (PSCs). An important finding is that there are strong orbital interactions between the conjugated organic spacer and adjacent inorganic layers, whereas no such interactions exist in DJ perovskite using an aliphatic octane-1,8-diaminium (ODA) spacer with similar length. The BThDMA spacer with multiple conjugated aromatic rings can also induce crystal growth with large grain size and preferred vertical orientation, resulting in reduced trap density and improved charge-carrier mobility. As a result, the optimized device based on (BThDMA)MAn -1 Pbn I3 n +1 (nominal n= 5) shows an excellent PCE of 18.1% with negligible hysteresis, which is a record efficiency for 2D DJ PSCs using a spacer with two or more covalently linked aromatic rings. These findings provide a novel and important insight on achieving efficient and stable 2D DJ perovskite solar cells by developing organic semiconductor spacers.

Reactivity, stability, and thermodynamics of para-methylpyridinium-based ionic liquids: Insight from DFT, NCI, and QTAIM

Ionic liquids (ILs) have lately piqued scientific attention due to their potential applications in green transition technologies such as catalysis, electrochemistry, and photovoltaic. The investigation of structural stability, reactivity, topological analysis, and thermodynamics of 4-methylpridine (4-picoline) based ILs is carried out using an advanced computational electronic structure theory technique based on first principle density functional theory (DFT). The ILs were modeled based on the interaction of 4-methylpridine (4-picoline) ion (cation) with borate, nitrate, phosphate, carbonate, and sulfate anions which have been chemically symbolized respectively as follows: [PMHP]+[HBO3]−, [PMHP]+[HNO3]−, [PMPH]+[HPO3]−, [PHMP]+[HCO3]−, and [PHMPM]+[HSO4]−. The energy difference between HOMO - LUMO of the studied compounds were found to show a general decreasing trend in the order: [PMHP][H2BO3] > [PMHP][NO3]> [PMPH][H2PO3]> [PHMP][HCO3]> [PHMPM][HSO4] with the borate ([PMHP][H2BO3]) and sulfate ([PHMPM][HSO4]) ILs having the relatively highest and least energy gap of 6.30 and 4.14 eV respectively. Strong interaction energies of 329.50 kca/mol, 114.41 kcal/mol, 107.12 kcal/mol, 98.19 kcal/mol and 87.86 kcal/mol involving the bonding, anti – bonding and lone pair orbitals associated with the pair of ILs were obtained as a trend: [PMHP][HSO4] > [PMHP][HCO3] > [PMPH][H2BO3] > [PHMP][NO3] > [PHMPM][H2PO3]. The intermolecular hydrogen bond (H-bond) analysis between the cation and anions ILs pairs obtained from quantum theory of atoms-in-molecules (QTAIM) reveals strong, weak, and electrostatic bonds. [PMPH]+[HSO4]− ILs pair was observed to possess the highest binding energy of -20.06 kcal/mol in the same way energy decomposition analysis (EDA) reveals a relatively strong orbital interaction in the [PMPH][HSO4] ILs due to the increase in electrostatic interaction of the four O-atoms in the sulfate anion, the analysis of the thermodynamic results indicates that the syntheses of the ILs are exothermic and spontaneous.

Nanoporous Intermetallic SnTe Enables Efficient Electrochemical CO2 Reduction into Formate via Promoting the Fracture of Metal-Oxygen Bonding.

Electrochemical reduction of CO2 into formate product is considered the most practical significance link in the carbon cycle. Developing cheap and efficient electrocatalysts with high selectivity for formate on a wide operated potential window is desirable yet challenging. Herein, nanoporous ordered intermetallic tin-tellurium (SnTe) is synthesized with a greater reduction performance for electrochemical CO2 to formate reduction compared to bare Sn. This nanoporous SnTe achieves 93% Faradaic efficiency for formate production and maintains over 90% Faradaic efficiency at a wide voltage range from -1.0 to -1.3V versus reversible hydrogen electrode (RHE), together with 60 h stability. Combining operando Raman spectroscopy studies with density functional theory calculations reveals that strong orbital interaction between Sn and neighboring tellurium (Te) in the intermetallic SnTe can lower the barriers of the oxygen cutoff hydrogenation and desorption steps by promoting the fracture of bond between metal and oxygen, leading to the significant enhancement of formate production.

Passivation principle of deep-level defects: a study of SnZn defects in kesterites for high-efficient solar cells

The strong molecular orbital interaction and the octet electron counting rule are realized simultaneously by the formation of 2PS + SnZn defect complex for passivating the deep-level of SnZn defect in kesterite solar cells.

Unexpected structures of the Au17 gold cluster: the stars are shining.

The Au17 gold cluster was experimentally produced in the gas phase and characterized by its vibrational spectrum recorded using far-IR multiple photon dissociation (FIR-MPD) of Au17Kr. DFT and coupled-cluster theory PNO-LCCSD(T)-F12 computations reveal that, at odds with most previous reports, Au17 prefers two star-like forms derived from a pentaprism added by two extra Au atoms on both top and bottom surfaces of the pentaprism, along with five other Au atoms each attached on a lateral face. A good agreement between calculated and FIR-MPD spectra indicates a predominant presence of these star-like isomers. Stabilization of a star form arises from strong orbital interactions of an Au12 core with a five-Au-atom string.

Acceleration Mechanisms of C–H Bond Functionalization Catalyzed by Electron-Deficient CpRh(III) Complexes

A rhodium(III) complex bearing a 1,3-bis(ethoxycarbonyl)-substituted or an unsubstituted cyclopentadienyl ligand (CpE or Cp) significantly accelerates a variety of oxidative C–H bond functionalization reactions. However, the driving force of the acceleration compared with a conventionally used Cp*Rh(III) complex has not been elucidated. Herein, we performed density functional theory (DFT) calculations of the rhodium(III)-catalyzed oxidative C–H bond olefination and annulation reactions using Cp*, Cp, and CpE ligands, which revealed that the CpERh(III) complex stabilizes transition states of not only a C–H bond activation step but also rate-determining reductive elimination and insertion steps by strong orbital interactions. For the sterically demanding substrates, the less sterically hindered CpRh(III) complex can stabilize the transition states of the reductive elimination step more than the CpERh(III) complex. Moreover, the whole reaction pathways were calculated to elucidate the mechanism and selectivity of the oxidative [4 + 2] and [2 + 2 + 2] annulation reactions under cationic and neutral conditions, respectively.

Enhanced photocatalytic efficiency by direct photoexcited electron transfer from pollutants adsorbed on the surface valence band of BiOBr modified with graphitized C

Herein, a novel BiOBr photocatalyst with partial surface modification by graphitized C (BiOBr-Cg) was synthesized through a hydrothermal method with hydrothermal carbonation carbon (HTCC) as a slow-releasing carbon source and characterized by experimental and theoretical methods. BiOBr-Cg exhibited excellent visible-light photocatalytic performance toward various refractory pollutants, such as bisphenol A, ibuprofen, ciprofloxacin, 2,4-dichlorophenoxyacetic acid, and diphenhydramine. The characterization results demonstrate that a strong molecular orbital interaction occurs between graphitized C and BiOBr, resulting in the formation of a new surface valence band on graphitized C. This not only promotes the oxidation of pollutants by surface holes but also reduces the recombination of carriers during the bulk phase transfer process, thereby increasing the number of photogenerated carriers. Intriguingly, the analytical results for degradation intermediates and other characterization techniques demonstrate that the pollutants adsorbed on the graphitized C of BiOBr-Cg can be directly excited through light irradiation and react along the organic radical degradation pathway in addition to pollutant degradation by holes and HO2•/O2•-.

Crystal facet-dependent frustrated Lewis pairs on dual-metal hydroxide for photocatalytic CO2 reduction

CO2 activation is a vital knot for CO2-mediated energy conversion and storage. Frustrated Lewis pairs (FLPs) are well confirmed to be highly efficient in CO2 activation. Here, we synthesized the single-crystal ZnSn(OH)6 cube with exposed (100) facet (Sc) and ZnSn(OH)6 octahedra with exposed (111) facet (So) and created FLPs with different acid-base distance on these exposed facets by vacuum irradiation, resulting from the light unstability of terminal hydroxyls. Our results demonstrated that the FLPs with short acid-base distance on So are more efficient activation centers due to the strong orbital interactions, well exemplifying that shortening the Lewis acid-base distance is a potential route to develop highly efficient FLPs catalysts. In addition, as an initial attempt, the combination effects between facet junction separating charges and FLPs activating molecules were proposed to accelerate CO2 reduction. Our findings may provide new insights into designing photocatalysts with highly catalytic performances.