RESUMO
2D carbon nitride nanosheets, exemplified by g-C3N4, offers significant structural benefits and enhanced photocatalytic activity. Nonetheless, the quantum confinement effect prevalent in nanoscale photocatalysts would result in an enlarged bandgap, potentially restricting the spectral absorption range and impeding improvements in photocatalytic efficiency. Here, a high-performance 2D photocatalyst with an extended spectral response is achieved by incorporating a novel phenol-like structure into the conjugated framework of ultrathin g-C3N4 nanosheet. This novel strategy features targeted pyrimidine doping to create a conjugated carbon zone in heptazine structure, offering a thermodynamically favorable pathway for hydroxyl functionalization during the annealing exfoliation process. Consequently, the π-π* transition energy in the material is significantly decreased, and the active lone pair electrons in phenol-like structure induces a new n-π* transition with notably enhanced absorption from 500 to 650 nm. The optimized material shows a dramatic enhancement in photocatalytic activity, achieving ≈72 times than the activity of bulk g-C3N4, and demonstrating a measurable H2 production rate of 6.57 µmol g-1 h-1 under 650 nm light. This study represents a significant step forward in the strategic design of 2D photocatalysts, with tailored electronic structures that significantly boost light absorption and photocatalytic efficiency.
RESUMO
Two new compounds namely [Zn(L1)phen]31 and Ni(L1)phen(MeOH) 2 (L1 = 3, 5-dichlorosalicylaldehyde thiosemicarbazone) were synthesized by the slow evaporation method at room temperature. The structure of ligand L1 was determined using 1H NMR and 13C NMR spectra. X-ray single crystal diffraction analysis revealed that compounds 1-2 can form 3D supramolecular network structures through π···π stacking and hydrogen bonding interactions. The DFT calculation shows that the coordination of ligand and metal is in good agreement with the experimental results. Hirshfeld surface analysis revealed that H H and Cl H interactions were the predominant interactions in compounds 1-2. Energy framework analysis indicated that dispersion energy played a dominant role in the energy composition of compounds 1-2. The inhibitory effects of compounds 1-2 against Escherichia coli (E. coli) and Methicillin-resistant Staphylococcus aureus (MRSA) were tested using the paper disk diffusion method (1: E. coli: 18 mm, MRSA: 17 mm, 2: E. coli: 15 mm, MRSA: 16 mm). Ion releasing experiments were conducted to assess the ion release capacity of compounds 1-2 (Zn2+, 4 days, 38.33 µg/mL; Ni2+, 4 days, 29.12 µg/mL). Molecular docking demonstrated the interaction modes of compounds 1-2 with UDP-N-acetylenolpyruvoylglucosamine reductase (MurB) and dihydrofolate reductase (DHFR) in bacteria, involving hydrophobic, stacking, hydrogen bonding and halogen bonding interactions. The generation of reactive oxygen species (ROS) in bacteria under the presence of compounds 1-2 were evaluated using a fluorescent dye known as dichlorodihydrofluorescein diacetate (DCFH-DA). Potential antibacterial mechanisms of compounds 1-2 were proposed.
Assuntos
Staphylococcus aureus Resistente à Meticilina , Antibacterianos/farmacologia , Escherichia coli , Ligantes , Simulação de Acoplamento Molecular , Zinco/farmacologia , Zinco/química , Níquel/química , Complexos de Coordenação/química , Complexos de Coordenação/farmacologiaRESUMO
BACKGROUND AND OBJECTIVE: In order to achieve early detection of myocardial ischemia and improve the diagnosis of coronary heart disease (CHD), it is necessary to find a convenient, non-invasive and effective examination method. This study aimed to explore the application value of dual-source computed tomography (CT) by using advanced modeled iterative reconstruction (ADMIRE) combined with computed tomography-fractional flow reserve (CT-FFR) technique in CHD, which provides imaging basis for early diagnosis of CHD and myocardial ischemia. METHODS: Seventy-five CHD patients were examined by coronary computed tomography angiography (CCTA). Their CCTA images were reconstructed by iterative algorithm in ADMIRE 1-5 using post-processing workstation. The standard deviation (SD), signal-to-noise ratio (SNR) and contrast-to-noise ratio (CNR) of proximal vascular images in right coronary artery (RCA), left main coronary artery (LM), left anterior descending artery (LAD) and left circumflex artery (LCX) were analyzed and compared. Invasive coronary angiography (ICA) was adopted in patients with ≥50% stenosis of coronary artery diameter. Taking ICA as the gold-standard method to accurately assess coronary arterial stenosis degree, the diagnostic efficiency of dual-source CT to diagnose coronary artery stenosis was analyzed. Some patients were subjected to myocardial CT perfusion (CTP) scanning and CT-FFR analysis, which facilitated analyzing the correlation and consistency between the diagnostic results of CTP and analysis results of CT-FFR. RESULTS: There was no statistical difference in the CT values of RCA, LM, LAD and LCX in groups with different ADMIRE reconstruction intensities (p > 0.05). But the noise, SNR and CNR interval were different among the iterative intensity groups (p < 0.05). Kappa consistency analysis was used to analyze the subjective evaluation results of image quality under different iterative reconstruction grades. The independent sample t-test performed on the subjective scores revealed that the scores on images were the best at ADMIRE 4. CCTA has sensitivity, specificity, positive predictive value, and negative predictive value of 91.52%, 97.59%, 97.98%, and 96.42% for identifying coronary artery stenosis, respectively. The diagnostic efficacy of CT-FFR, the Kappa analysis of myocardial CTP and CT-FFR results, which yields a Kappa value of 0.830 (p < 0.05). Spearman correlation analysis was used to statistically analyze the results of myocardial CTP and CT-FFR (correlation coefficient r = 0.774, p < 0.05). Diagnostic sensitivity and specificity were 93% and 95%, respectively. CONCLUSIONS: The dual-source CT using ADMIRE iterative algorithm has the best display of coronary vessels and higher image quality when the intensity is 4, and CT-FFR can be used as a non-invasive method for early detection of myocardial ischemia, which is worthy of clinical application.
Assuntos
Doença da Artéria Coronariana , Estenose Coronária , Reserva Fracionada de Fluxo Miocárdico , Isquemia Miocárdica , Humanos , Constrição Patológica , Angiografia Coronária/métodos , Tomografia Computadorizada por Raios X , Estenose Coronária/diagnóstico por imagem , Valor Preditivo dos Testes , Estudos RetrospectivosRESUMO
Adsorptive separation using porous materials is a promising approach for separating alkynes/olefins due to its energy efficiency, while the deep removal of trace amounts of C2H2 and CO2 from C2H4 is still very challenging for a commercial adsorbent. Herein, we report a low-cost inorganic metal cation-mediated mordenite (MOR) zeolite with the specific location and distribution of K+ cations acting as a goalkeeper for accurately controlling diffusion channels, as evidence of the experimental and simulation results. Deep purification of C2H4 from ternary CO2/C2H2/C2H4 mixtures was first realized on K-MOR with exceptional results, achieving a remarkable polymer-grade C2H4 productivity of 1742 L kg-1 for the CO2/C2H2/C2H4 mixture. Our approach which only involves adjusting the equilibrium ions, is both promising and cost-effective, and opens up new possibilities for the use of zeolites in the industrial light hydrocarbon adsorption and purification process.
RESUMO
To date, precisely tailoring local active sites of well-defined earth-abundant metal-free carbon-based electrocatalysts for attractive electrocatalytic oxygen reduction reaction (ORR), remains challenging. Herein, the authors successfully introduce a strain effect on active C-C bonds adjacent to edged graphitic nitrogen (N), which raises appropriate spin-polarization and charge density of carbon active sites and kinetically favor the facilitation of O2 adsorption and the activation of O-containing intermediates. Thus, the constructed metal-free carbon nanoribbons (CNRs-C) with high-curved edges exhibit outstanding ORR activity with half-wave potentials of 0.78 and 0.9 V in 0.5 m H2 SO4 and 0.1 m KOH, respectively, overwhelming the planar one (0.52 and 0.81 V) and the N-doped carbon sheet (0.41 and 0.71 V). Especially in acidic media, the kinetic current density (Jk ) is 18 times higher than that of the planar one and the N-doped carbon sheet. Notably, these findings show the spin polarization of the asymmetric structure by introducing a strain effect on the C-C bonds for boosting ORR.
RESUMO
Cu-exchanged low-silica CHA zeolites (Si/Al≤4) synthesized without organic templates are promising candidate catalysts for ammonia selective catalytic reduction of nitrogen oxides (NH3 -SCR), but their practical application is restricted due to the low hydrothermal stability. Here, inspired by the transcription from duplex DNA to RNA, we synthesized Al pairs enriched low-silica CHA zeolite (CHA-SPAEI, Si/Al=3.7) by using silicoaluminophosphate (SAPO) featured by strict alternation of -Al-O-P(Si)-O-Al-O- tetrahedra as seed. The proportion of Al pairs in CHA-SPAEI is 78 %, which is much higher than that in the conventional low-silica CHA (CHA-LS, 52 %). After hydrothermal ageing at 800 °C for 6â h, Cu-exchanged CHA-SPAEI shows NO conversion above 90 % within 225-500 °C under a gas hourly space velocity of 200,000â h-1 , which is much better than that of Cu-exchanged CHA-LS. The spatial close proximity of Al pairs in CHA-SPAEI is confirmed by the 27 Al double-quantum single-quantum two-dimensional NMR analyses. The strict -P(Si)-O-Al-O-P(Si)-O- sequence in the fragments from the dissolution of SAPO seed promotes the Al pairs with the -Al-O-Si-O-Al-O- sequence via a transcription process. The utilization of aluminophosphate-based zeolites as seeds opens up a new avenue for the regulation of the Al distribution in zeolites.
RESUMO
Metallic conductive 1T phase molybdenum sulfide (MoS2 ) has been identified as promising anode for sodium ion (Na+ ) batteries, but its metastable feature makes it difficult to obtain and its restacking during the charge/discharge processing result in part capacity reversibility. Herein, a synergetic effect of atomic-interface engineering is employed for constructing 2H-MoS2 layers assembled on single atomically dispersed Fe-N-C (SA Fe-N-C) anode material that boosts its reversible capacity. The work-function-driven-electron transfer occurs from SA Fe-N-C to 2H-MoS2 via the Fe-S bonds, which enhances the adsorption of Na+ by 2H-MoS2 , and lays the foundation for the sodiation process. A phase transfer from 2H to 1T/2H MoS2 with the ferromagnetic spin-polarization of SA Fe-N-C occurs during the sodiation/desodiation process, which significantly enhances the Na+ storage kinetics, and thus the 1T/2H MoS2 /SA Fe-N-C display a high electronic conductivity and a fast Na+ diffusion rate.
RESUMO
Zeolites are typically a class of crystalline microporous aluminosilicates that are constructed by SiO4 and AlO4 tetrahedra. Because of their unique porous structures, strong Brönsted acidity, molecular-level shape selectivity, exchangeable cations, and high thermal/hydrothermal stability, zeolites are widely used as catalysts, adsorbents, and ion-exchangers in industry. The activity, selectivity, and stability/durability of zeolites in applications are closely related to their Si/Al ratios and Al distributions in the framework. In this review, we discussed the basic principles and the state-of-the-art methodologies for regulating the Si/Al ratios and Al distributions of zeolites, including seed-assisted recipe modification, interzeolite transformation, fluoride media, and usage of organic structure-directing agents (OSDAs), etc. The conventional and newly developed characterization methods for determining the Si/Al ratios and Al distributions were summarized, which include X-ray fluorescence spectroscopy (XRF), solid state 29Si/27Al magic-angle-spinning nuclear magnetic resonance spectroscopy (29Si/27Al MAS NMR), Fourier-transform infrared spectroscopy (FT-IR), etc. The impact of Si/Al ratios and Al distributions on the catalysis, adsorption/separation, and ion-exchange performance of zeolites were subsequently demonstrated. Finally, we presented a perspective on the precise control of the Si/Al ratios and Al distributions of zeolites and the corresponding challenges.
RESUMO
Solid state electrolytes have been intensively studied in the solid oxide fuel cells (SOFCs). The aim of this work is to investigate the effects of MgO and Fe2O3 dual sintering aids on the microstructure and electrochemical properties of solid state Gd0.2Ce0.8O2-δ (GDC) electrolytes, which are prepared by a sol-gel method with MgO and Fe2O3 addition to the GDC system. It is found that the addition of MgO and Fe2O3 can reduce the sintering temperature, increase densification and decrease the grain boundary resistance of the electrolyte. The 2 mol% MgO and 2 mol% Fe2O3 co-doped GDC (GDC-MF) exhibits the highest grain boundary conductivity. At 400°C, the grain boundary conductivity and total conductivity of GDC-MF are 15.89 times and 5.56 times higher than those of GDC. The oxygen reduction reaction (ORR) rate at the electrolyte/cathode interface of GDC-MF is 47 % higher than that of GDC. Furthermore, the peak power density of a single cell supported by GDC-MF is 0.45 W cm-2 at 700°C, 36.7% higher than that of GDC. Therefore, the GDC-MF should be a promising electrolyte material for intermediate-temperature solid oxide fuel cells (IT-SOFCs).
RESUMO
In recent decades, the application of zeolite has been extended to many sustainable processes. Professor Ruren Xu () of Jilin University is a leader within Chinese, Asian and worldwide zeolite communities, as well as the founder of the inorganic synthesis discipline in China and the first person in the world to propose the scientific discipline of modern inorganic synthetic chemistry. Professor Xu started his scholarly research on zeolites in the mid-1970s. He focused initially on crystallization and mechanisms of zeolite formation. In the 1980s, he gradually shifted his research to the exploration of microporous materials with novel frameworks and compositions. In 1984, he outlined new directions in the synthesis of zeolites and placed emphasis on the 'heteroatom concept', which turned out to be very influential and fruitful for the subsequent development of heteroatom-containing zeolite catalysts. In the following years, he and his group systematically developed new solvothermal routes for zeolite synthesis. In the late 1990s, Xu started to think about the rational synthesis of zeolites, a major challenge for zeolite as well as inorganic synthesis in general. His group developed several effective strategies for the rational design and synthesis of zeolitic materials. He is the chairman of the 15th International Zeolite Conference (15th IZC) held in 2007 for the first time in China. Because of his significant contribution to zeolite science in China, he received the National Zeolite Lifetime Achievement Award of China in 2017. NSR recently interviewed Professor Xu about the current status and future prospects of zeolites and related porous materials. This interview is dedicated to Professor Xu on his 90th birthday, in recognition of his seminal contribution to zeolite science, modern inorganic synthetic chemistry and the new discipline of condensed matter chemistry, which was first suggested by Professor Xu in 2018.
RESUMO
Separation of mixture is always necessarily required in modern industry, especially in fine chemical, petrochemical, coal chemical and pharmaceutical industries. The challenge of the separation process is usually associated with small molecules with very similar physical and chemical properties. Among the separation techniques, the commonly used high-pressure cryogenic distillation process with combination of high pressure and very low temperature is heavily energy-consuming, which accounts for the major production costs as well as 10-15% of the world's energy consumption. To this end, the adsorptive separation process based on zeolite sorbents is a promising lower-energy alternative and the performance is directly determined by the zeolite sorbents. In this review, we surveyed the separation mechanisms based on the steric, equilibrium, kinetic and 'trapdoor' effect, and summarized the recent advances in adsorptive separation via zeolites including CO2, light olefins, C8 aromatics and hydrogen isotopes. Furthermore, we provided the perspectives on the rational design of zeolite sorbents for the absolute separation of mixtures.
RESUMO
Water pollutants existing in their oxyanion forms have high solubility and environmental mobility. To capture these anionic pollutants, cost-effective inorganic materials with cationic frameworks and outstanding removal performance are ideal adsorbents. Herein, we report that two-dimensional (2D) cationic aluminoborate BAC(10) sets a new paradigm for highly selective and efficient capture of Cr(VI) and other oxyanions from aqueous solution. The structure of Cr(VI)-exchanged BAC(10) sample (Cr(VI)@BAC(10), H0.22·Al2BO4.3·(HCrO4)0.22·2.64H2O) has been successfully solved by continuous rotation electron diffraction. The crystallographic data show that the 2D cationic layer of BAC(10) is built by AlO6 octahedra, BO4 tetrahedra, and BO3 triangles. Partial chromate ions exchanged with Cl- ions are located within the interlayer region, which are chemically bonded to the aluminoborate layer. BAC(10) shows faster adsorption kinetics compared to the commercial anion exchange resin (AER) and layered double hydroxides (LDHs), a higher maximum adsorption capacity of 139.1 mg/g than that of AER (62.77 mg/g), LDHs (81.43 mg/g), and a vast majority of cationic MOFs, and a much broader working pH range (2-10.5) than LDHs. Moreover, BAC(10) also shows excellent Cr(VI) oxyanion removal performance for a solution with a low concentration (1-10 mg/L), and the residual concentration can be reduced to below 0.05 mg/L of the WHO drinking water criterion. These superior properties indicate that BAC(10) is a promising material for remediation of Cr(VI) and other harmful oxyanions from wastewater.
RESUMO
Electrocatalytic oxygen reduction reaction (ORR) and oxygen evolution reduction (OER) are regarded as the key reactions via the sustainable system (fuel cell and water splitting), respectively. In OER, the transition from singlet oxygen species to triplet oxygen molecules is involved, meanwhile the ORR involves the transition from triplet oxygen molecules to singlet oxygen species. However, in these processes, the number of unpaired electrons is not conserved, which is not thermodynamically favorable and creates an additional energy barrier. Fortunately, regulating the electrocatalysis by spin-state modulation enables a unique effect on the catalytic performance, but the current understanding on spin-state engineering for electro-catalyzing ORR and OER is still insufficient. Herein, this review summarized the in-spin engineering for the state-of-the-art ORR and OER electrocatalysts. It began by introducing engineering of spin-state to egfilling for ORR and OER process, and then moved to spin polarization and spin-pinning effect for OER process. Various designed strategies focusing on how to regulate the spin-state of the active center have been summarized up. The connectivity of the structures of typical ORR (e.g. metal-nitrogen-carbon) and OER (e.g. design strategies oxides, metal organic frameworks) catalysts depending on the spin level is also discussed. Finally, we present the outlook from the aspects of template catalysts, characterization methods, regulation strategies, theoretical calculations, which will further expand the possibility of better electrocatalytic performance through spin-state modulation. This review concluded some open suggestions and prospects, which are worthy of the community's future work.
RESUMO
Capturing volatile radionuclide iodine produced in the nuclear industry is a crucial environmental issue. In previous studies, the principal efficient adsorbent for iodine capture was silver-containing zeolite. As silver-containing zeolites are expensive, alternate copper-loaded porous zeolites, including CuCl loaded NaY reduced by H2 (denoted as H2CuY) and CO (denoted as COCuY), were studied for iodine adsorption at moderate temperatures. The current work also discusses the influence of copper valency on iodine adsorption. Due to the copper sites and nanosized pore structure, H2CuY and COCuY showed high iodine adsorption capacities of 450 and 219 mg/g, respectively. The iodine adsorption capacity of H2CuY was higher than that of silver-loaded zeolites. Moreover, H2CuY and COCuY adsorbed volatile iodine through a chemical mechanism involving the copper sites of different valencies, and the Cu0 was more effective in adsorbing iodine than Cu+. These copper-loaded zeolites with strong chemical interactions with iodine and high iodine adsorption capacities provided the possibility for iodine adsorption application in the nuclear industry.
RESUMO
Degradability is a key safety issue when choosing materials for biomedical applications and environmental protection. This factor greatly limits the application of porous carbon in these areas due to the inert and stable nature of carbon network. In this work, this conflict could be well-resolved by rational designing a mesoporous carbon (MC) with biomass as a carbon source. The retained oxygen-containing species simultaneously increase drug adsorption capacity and the degradability of MC. The maximum adsorption quantity for doxorubicin over MC can reach 395.3 mg/g, about 3-fold over carbon nanotubes. The detailed analysis reveals that the degradation of MC occurs via a radical mediated oxidation process. The high electron density feature of MC facilitates the electrophilic addition reaction in the presence of HO. During this process, the carbon network is gradually degraded into fragments, carbon nanodots and ultimately to CO2. This work opens up a new way to fabricate degradable porous materials and provides a promising material for the practical application in biomedical and environmental field.
Assuntos
Nanotubos de Carbono , Adsorção , Biomassa , PorosidadeRESUMO
Enhancing the stability of the resin-dentin bonding interface via simultaneously improving the antibacterial, mechanical, and adhesive properties of a dental adhesive is the key to prolonging the longevity of dental restoration for caries treatment. Herein, we present the stabilization effect of Ag+- and Zn2+-exchanged zeolite A (denoted as Ag-A and Zn-A, respectively) on the resin-dentin bonding interface. Ag-A and Zn-A zeolites exhibited sustained ion release capability, outstanding biocompatibility to L929 cells (<2 mg/mL), and excellent antibacterial ability to Streptococcus mutans (minimum inhibitory concentration: 100 µg/mL for Ag-A and 200 µg/mL for Zn-A). One-step self-etching adhesives modified by Ag-A, Zn-A, or Ag-/Zn-A (1/1 in weight) zeolites with an ultralow loading of 0.2 wt % exhibited favorable antibacterial activity with the inhibition of biofilm formation by 70.33, 56.47, and 62.54%, respectively. Compared to the control group, Zn-A- and Ag-/Zn-A-modified adhesives significantly increased the wettability properties of the adhesive and the long-term resin-dentin bond strength (by â¼25%) after 5000 thermocycles of aging. The current data demonstrated that the introduction of 0.2 wt % Zn-A or Ag-/Zn-A into the adhesive remarkably enhanced the stability of the resin-dentin bonding interface. Our findings provide a new strategy to modify the dental adhesive for further optimizing the longevity of dental restorations for caries.
Assuntos
Cimentos de Resina , Zeolitas , Antibacterianos/farmacologia , Dentina , Teste de Materiais , Cimentos de Resina/química , Cimentos de Resina/farmacologia , Zeolitas/farmacologia , Zinco/farmacologiaRESUMO
High dosage of expensive Pt to catalyze the sluggish oxygen reduction reaction (ORR) on the cathode severely impedes the commercialization of proton exchange membrane fuel cells. Therefore, it is urgent to cut down the Pt catalyst by efficiently improving the ORR activity while maintaining high durability. Herein, magic concave Pt-Zn nanocubes with high-index faceted Pt skin (Pt78 Zn22 ) are proposed for high-efficiency catalysis toward proton exchange membrane fuel cells. These unique structural features endow the Pt-skin Pt78 Zn22 /KB with a mass activity of 1.18 mA µgPt -1 and a specific activity of 3.64 mA cm-2 for the ORR at 0.9 V (vs RHE). Meanwhile, the H2 -O2 fuel cell assembled by this catalyst delivers an ultrahigh peak power density of ≈1449 mW cm-2 . Both experiments and theoretical calculations show that the electronic structure of the surface is adjusted, thereby shortening the length of the Pt-Pt bond and reducing the adsorption energy of OH*/O* on the Pt surface. This work demonstrates the synergistic effect of the oxidation-resistant metal Zn and the construction of Pt-rich surface engineering. Also, it guides the future development of catalysts for their practical applications in energy conversion technologies and beyond.
RESUMO
Improving proton conductivity and fabricating viable metal-organic frameworks (MOFs) based proton exchange membranes (PEMs) are central issues exploiting electrolyte MOFs. We aim to design multivariate flexibility synergistic strategy to achieve Flexible MOFs (FMOFs) with high conductivity at a wide range of humidity. In situ powder X-ray diffraction (PXRD) and temperature-dependent Fourier transform infrared spectra (FT-IR) prove the synergistic self-adaption between dynamic torsion of alkyl sulfonic acid and dynamic breathing of FMOF, forming a continuous hydrogen-bonding networks to maintain high conductivity. Based on the convincing proton conductivity, we construct a series of long-term durable MOF-based PEMs that serve as a bridge between MOF and fuel cell. Consequently, the membrane electrode assembly (MEA) of the flexible PMNS1-40 exhibits a maximum single-cell power density of 34.76â mW cm-2 and hopefully opens doors to evaluate the practical application of proton-conducting MOFs in direct methanol fuel cells.
RESUMO
Functional nanoporous materials are widely explored for CO2 separation, in particular, small-pore aluminosilicate zeolites having a "trapdoor" effect. Such an effect allows the specific adsorbate to push away the sited cations inside the window followed by exclusive admission to the zeolite pores, which is more advantageous for highly selective CO2 separation. Herein, we demonstrated that the protonated organic structure-directing agent in the small-pore silicoaluminophosphate (SAPO) RHO zeolite can be directly exchanged with Na+, K+, or Cs+ and that the Na+ form of SAPO-RHO exhibited unprecedented separation for CO2/CH4, superior to all of the nanoporous materials reported to date. Rietveld refinement revealed that Na+ is sited in the center of the single eight-membered ring (s8r), while K+ and Cs+ are sited in the center of the double 8-rings (d8rs). Theoretical calculations showed that the interaction between Na+ and the s8r in SAPO-RHO was stronger than that in aluminosilicate RHO, giving an enhanced "trapdoor" effect and record high selectivity for CO2 with the separation factor of 2196 for CO2/CH4 (0.02/0.98 bar). The separation factor of Na-SAPO-RHO for CO2/N2 was 196, which was the top level among zeolitic materials. This work opens a new avenue for gas separation by using diverse silicoaluminophosphate zeolites in terms of the cation-tailored "trapdoor" effect.