马 超，刘晓娜，乜晨阳，陈 陆，田 鹏，徐弘毅，郭 鹏，刘中民

（1.中国科学院大连化学物理研究所甲醇制烯烃国家工程实验室,国家能源低碳催化与工程研发中心,洁净能源国家实验室,大连116023；2.中国科学院大学,北京100049；3.大连理工大学张大煜学院,大连116024；4.赛默飞世尔科技(中国)有限公司,上海201203；5.斯德哥尔摩大学材料与环境化学学院,斯德哥尔摩SE⁃106 91,瑞典）

1 Introduction

Zeolites are microporous crystalline materials with well-defined channels or cavities. It consists of tetrahedral TO4as thebasic building unit，where T atoms can be Si，Al，Ge，B，etc. Until now，there are 252 zeolites or zeolite related materials that have been approved and assigned three-letter framework type codes（FTCs）by International Zeolite Association’s Structure Commission［1，2］. Due to their unique acid properties，tunable pore sizes，and excellent hydrothermal stabilities，they are widely used in adsorption，separation，and catalysis［3，4］. Knowing their structural information at the atomic level is important for understanding their physi⁃cal and chemical properties，in turn facilitating the exploration of their applications. Moreover，investigating the behavior of guest species such as structure-directing agents（SDAs）and adsorbed molecules in the pores of zeolites can also help researchers to synthesize new zeolites or modify known zeolites with desired properties.Therefore，it is of significance to characterize crystallographic structures of zeolites.

X-ray diffractometer and transmission electron microscopy（TEM）are considered as powerful tools for unraveling the structural information of zeolites，such as the periodic structures of new zeolites，the local nonperiodic atomic information（defects，surface，interface，disorder，etc.），locations of exotic elements within zeolite frameworks and guest species occluded in channels or cavities［5—28］. Conventionally，single-crystal X-ray diffraction（SXRD）and powder X-ray diffraction（PXRD）are two common techniques for studying zeo⁃lite structures. Diffraction data collected by both methods can be utilized for the structure solution and refine⁃ment. Typically，zeolite crystals of interest have to be larger than 20 μm and 500 nm for SXRD and PXRD investigations，respectively. It is worth pointing out that PXRD technique，which is widely used for simple phase identifications in our daily scientific researches，has shown its power in exploring the complex zeolite structure and probing host-guest interactions［5，13，15，16，28］. If the crystal is too small even down to nanometer，structural investigations by TEM can provide structural information at the atomic level through exploring diffraction in reciprocal space and imaging in real space. In its diffraction mode，conventional selected area electron diffraction（SAED）［two-dimensional（2D）information］can be used to distinguish amorphous and crystalline regions，determine the orientation of crystals，facilitate repartition of intensities from the overlap⁃ping reflections in PXRD，etc.［26，27］，while the newly developed three-dimensional（3D）electron diffraction can be processed to obtain the unit cell parameters，space group，and structure determination，which will be discussed in detail. Furthermore，high-resolution TEM（HRTEM）imaging，high angle annular dark-field（HAADF）scanning transmission electron microscopy（STEM），integrated differential phase contrast（iDPC）can be used for visualizing the local structure at atomic resolution，such as disorder and defects［6，12，14，19，23］.

In this review，we firstly introduce several structural characterization techniques for known and unknown zeolites. Secondly，we summarize and categorize 85 new zeolites discovered since 2007. Based on the uniqueness of synthetic methodologies or structural characteristics，nine novel zeolites are selected for the fur⁃ther discussions.

2 Zeolite Structural Characterization Techniques

2.1 Single Crystal X-ray Diffraction

When monochromatic X-ray illuminates a crystalline sample，it produces constructive interference and diffracted X-ray，satisfying Bragg’s law：nλ= 2dsinθ，wherenis an integer，λis the wavelength of the monochromatic X-ray，dis interplanar spacing generating diffraction，andθis the diffraction angle［29］. Digi⁃tized detectors are used for recording these diffracted X-rays. By changing orientations of the crystal and the position of detector，3D discrete X-ray diffracted spots in reciprocal space can be collected［Fig.1（A）］. Then，we can index these discrete diffracted spots and extract their intensities，which can then be used for structure determination. Initial structure models will be obtained by utilizing phasing algorithms［30，31］and the structure model is further refined against SXRD data. For instance，Gaoet al.has determined the structure of NUD-2（FTC：*CTH）and identified locations of Ge and F atoms by SXRD［Fig.1（B）］［7］. However，this approach has the strict criterion of crystal size as mentioned before. Nanocrystals are too small to be studied by this approach.

Fig.1 STOE SXRD(left)and its schematic illustration(right)(A)and Ge and F atoms located in NUD⁃2(B)

2.2 Powder X-ray Diffraction

When X-ray illuminates a large number of crystals（random orientations），the discrete diffracted spots are superimposed forming diffracted rings，compressing 3D structural information in reciprocal space into 1D diffraction spectrum. This will inevitably cause the overlap of diffraction peaks. Conventionally，synchrotron PXRD data has been widely used for determining the structure of unknown zeolite. For example，Honget al.［15］solved the structure of EU-12（ETL）using synchrotron PXRD data. Since the beamtime of synchro⁃tron PXRD is not easy to apply，our group has installed STOE STADI P ESSENTIAL diffractometer equipped with a Mythen II detector to collect high quality in-house PXRD. STOE diffractometer uses a curved crystal monochromator to produce a stable convergent X-ray beam of pure CuKα1radiation. The peak positions are not biased by anyKα2component，and consequently the resolution of the remaining peaks is improved. More⁃over，STOE instrument adopts the capillary mode in the Debye-Scherrer transmission geometry. Its advantages are listed as follows：1）Capillary samples are nearly unaffected by effects of preferred orientation. 2）There is no suffering from height displacement as known from reflection samples. 3）Micro-sampling is possible，if only very small volumes of sample material are available［32］. Recently，our group has utilized in-house high quality PXRD data collected from STOE diffractometer to develop a new synthetic methodology allowing targeted synthesis of zeolites，determination of guest inorganic cations，and unraveling the distribution of Al in zeolites.

The first example is developing a novel approach for facilitating the targeted synthesis of zeolitic silicoaluminophosphates（SAPOs）by studying locations and interactions of organic SDAs（OSDAs）revealed from PXRD data［5］. DNL-6（SAPO form RHO topology）was first reported by our laboratory in 2011［33］. It could only be synthesized by diethylamine（DEA）andN，N′-dimethylethylenediamine（DMEDA）before 2018. We explored an approach called RSS（Refine，Summarize，and Search）to assist its targeted synthesis.This approach contains three steps：1）Refine the known as-made DNL-6 templated by DEA and DMEDA against PXRD data. 2）Based on the understanding of locations and interactions of DEA and DMEDA，sum⁃marize the common structural roles of DEA and DMEDA in DNL-6 samples. 3）Search for other commercial OSDAs with the same structural features for the targeted synthesize of DNL-6s. Utilizing this methodology，we found another nine types of OSDAs for DNL-6［Fig.2（A）］. Apart from DNL-6，RSS approach was further employed to explore the synthesis of SAPO-42（SAPO form LTA topology）［28］. We synthesized SAPO-42 in the fluoride-free system for the first time and extend the OSDAs from“symmetric”secondary amines to a series of“asymmetric”ones［Fig.2（A）］. Moreover，the locations of Cu2+in SAPO-42 catalyst for NH3-SCR reaction was also revealed by Rietveld refinement against PXRD data.

Fig.2 An RSS approach facilitating the targeted synthesis of DNL⁃6 and SAPO⁃42(A); in the as⁃made FER zeolite(blue: Al or Si atom, red: O atom), unprotonated pyridine located in the fer cage(B)and 10⁃ring channel(C), respectively; Na+ ion is in the 10⁃ring channel only（D); in the pyridine⁃adsorbed sample, the protonated pyridine is occluded in the 10⁃ring channel and forms hydrogen bonding with framework oxygen O2(E)[16]

The second example is the identification of Al sites in zeolites，which is closely related to distributions of Brønsted acids（—Al—OH—Si—）. We select aluminosilicate ferrierite（FER）（Si/Al=26）as an example for illustration［16］. Since Si4+and Al3+are isoelectronic，they cannot be distinguished by PXRD directly. We tried to explore the Al-rich positions by analyzing the refinement results of as-made and pyridine（Py）-adsorbed sam⁃ples. Rietveld refinement results of the as-made sample suggested that unprotonated Py locate in the 10-ring channels andfercages，while Na+are identified in the 10-ring channels solely，balancing the negative charges［Fig.2（B）—（D）］. Since Na+ion is close to the T1 site，implying that T1 is an Al-rich position. In the Py-adsorbed sample，the probe molecule Py is located in the 10-ring channel and forms hydrogen bonding with O2，confirming that T1 is the Al-rich position［Fig.2（E）］.

2.3 3D Electron Diffraction

Laue found X-ray can interact with crystals forming diffraction in 1912. The diffraction of electrons（charged particles）by crystals was later discovered by C. J. Davisson and G. Thompson，who shared the Nobel Prize in 1937［34］. The main advantage of electron crystallography is that 3D electron diffraction data can be obtained from crystals too small for SXRD. Apart from the different wavelength of the incident beam and distinct interactions with matters，3D electron diffraction shares similar technical aspects to SXRD. In the late 2000s，Zouet al.［35，36］and Kolbet al.［37，38］developed methods for automated collection and processing of 3D electron diffractions，called rotation electron diffraction（RED）and automated diffraction tomography（ADT）respectively. Here，we introduce RED as an example. As shown in Fig.3（A），the rotation of crystal is achieved by combining fine electron beam tilts（typically in 0.1° steps）and coarse goniometer tilts（typically in 2°steps）［36］. We collect 2D electron diffraction patterns at each combined tilt angle. These electron diffrac⁃tion patterns are further processed to reconstruct the 3D reciprocal lattice of the crystal. The unit cell parame⁃ters and space group can then be deduced from the reconstructed lattice. The intensities of indexed diffraction spots can be extracted and used for structure determination. Recently，a new approach called continuous rota⁃tion electron diffraction（cRED）was developed，which is an updated version of RED technique［39］. In cRED，the crystal is continuously rotated in the electron beam while electron diffraction patterns are collected simulta⁃neously with a fast detector. There are two significant improvements in this updated technique. Firstly，the collection time and overall electron dose can be greatly reduced. This is especially useful for working with electron-beam sensitive materials. Secondly，it has been demonstrated that cRED offered a great improvement in electron data quality，which is attributed to the 3D integration of diffraction intensities. This makes the structure determination（structure solution and structure refinement）of beam sensitive material such as metalorganic framework and proteins possible［40，41］. Since 2007，17 new zeolites have been solved using RED/cRED，while one zeolite have been solved by a combination of RED/cRED with other techniques. For in⁃stance，the newly accepted EMM-37（ETV）and SYSU-3（-SYT）were all solved using cRED alone［11，18］.

Fig.3 Schematic illustration of RED method(A)[36];HRTEM images of a thin edge(B)and broken crystal piece(C)of Beta⁃TEAOH[23];low magnification TEM image of ZSM⁃57⁃Na(D);HRTEM images of the highlighted orange area(E)and isolated fragment from the same sample(F)[27]

2.4 High-Resolution Transmission Electron Microscopy(HRTEM)

HRTEM，which illuminates the specimen with parallel electron beam and uses camera to record the phase contrast，is one of the most common techniques to study zeolite structure in real space. Compared with the aforementioned diffraction methods（SXRD，PXRD，RED/ADT），HRTEM imaging can provide local infor⁃mation of zeolite structures. Thus，it is a powerful tool for investigating disorders and defects. For instance，the chiral polymorph A-enriched zeoliteBetawas confirmed by HRTEM images and enriched polymorph A and B domains were also revealed［Fig.3（B），（C）］［23］. Moreover，structural information including structure factor amplitudes and phases can be extracted from HRTEM images，which can be further utilized for structure solu⁃tion. For example，Willhammaret al.［19］found stacking faults in ITQ-39（*-ITN）from HRTEM images. A 3D electrostatic potential map was calculated from the combined structural information extracting from different projections of HRTEM images. Utilizing this approach，they obtained the crystallographic structure of ITQ-39 Polymorph B，and then ITQ-39A and ITQ-39C were built based on the stacking sequence［19］. Apart from solving the structure solely，the structure factor phases extracted from HRTEM images can also be applied to PXRD data for the establishment of initial structural model. By combining the PXRD data and HRTEM images，the complex zeolite TNU-9（TUN）was solved［13］. It is worth noting that the contrast of HRTEM images，which is heavily affected by the defocus of the objective lens，should be interpreted cautiously.HRTEM images can not only be utilized for solving novel zeolite structures as mentioned before but also for investigating twin features in known zeolites. For instance，we studied the twin in ZSM-57（MFS）through HRTEM and RED systematically. As shown in Fig.3（D）—（F），ZSM-57-Na share｛0kk｝crystallographic faces in real space. The twin boundary andab-planes exposed exterior are highlighted［27］.

2.5 High Angle Annular Dark Field(HAADF)and Integrated Differential Phase Contrast(iDPC)

Different from the aforementioned HRTEM mode，scanning transmission electron microscopy（STEM）mode，which uses convergent electron beam to scan the specimen point by point，is another commonly used imaging method. Among all the signals acquired from the STEM mode，high-angle scattered electrons，which follow the Rutherford scattering mechanism，generate HAADF images as shown in Fig.4（A）［42］. Since HAADF imaging is incoherent and its contrast is approximately proportional toZ2，whereZis the atomic number，the contrast of HAADF images is sensitive to heavy elements，making it possible to identify heavy metal atoms in zeolite frameworks. Furthermore，it is also much easier to interpret the contrast of HAADF images compared to that of HRTEM images. For instance，site-isolated platinum in KLTL（LTL）was directly visualized by this technique using aberration-corrected TEM［Fig.4（B）］［6］. In recent years，an emerging STEM imaging technique named iDPC has been developed［43］. This novel imaging method makes use of a segmented detector，which is divided into four quadrants［Fig.4（A）］，to collect almost all the transmitted electrons and integrate the vector electric field of the sample calculated from the signal of different quadrants.For non-magnetic thin samples，iDPC image is directly interpretable as the projected electrostatic potential，and leads to a contrast roughly proportional to the atomic numberZ. Thus，iDPC can image both light and heavy elements better than HAADF. Since iDPC utilizes transmitted electrons，it can obtain images with a higher signal-to-noise ratio under the low dose imaging condition compared with HAADF. Therefore，it is a more powerful technique to image beam sensitive materials such as zeolites or MOFs［12，14］. Recently，Weiet al.［12］has visualized the local structures of ZSM-5（MFI），such as terminations of different surfaces，interfaces in assemblies，and adsorbed para-xylenes（PX）［Fig.4（C）—（H）］. Hanet al.［14］has also imaged the atomically dispersed Mo atoms directly［Fig.4（I）］，which enables us to probe the locations of Al atoms in ZSM-5.

Fig.4 Schematic illustration of STEM system(A)[42]; HAADF image of site⁃isolated Pt atoms in KLTL zeolite in the oxidized sample(B)[6]; iDPC images of the surface terminations from the[010]direction in the ZSM⁃5(C—F);iDPC image of the(010)interfaces between ZSM⁃5 particles(G); iDPC image of the PX⁃adsorbed ZSM⁃5 from the [010] direction(H)[12] and iDPC image of Mo/ZSM⁃5(I)[14]

3 Several Types of Zeolites with New Framework Type Codes(FTCs)

Seventy-six novel zeolite framework type codes have been approved by the International Zeolite Associa⁃tion’s Structure Commission since the 6th edition of Atlas of Zeolite Framework Types was released in 2007.As far as we know，there were also 9 novel zeolites without framework type codes. Through careful inspec⁃tions，we found that there are 14 pure-silica zeolites，20 aluminosilicates，24 germanosilicates，and 6 borosili⁃cates among these ones（Table 1）. By analyzing and summarizing synthetic methodologies，structure determi⁃nation approaches，and structural characteristics of these new zeolites，we selected the following types of fea⁃tured work for detailed illustrations.

3.1 From ITQ-29(pure-silica LTA)to ITQ-50(pure-silica IFY)

Under a high pressure of 3.2 GPa，the pure-silica zeolite ITQ-29（LTA）underwent an order-to-order reconstructive phase transition，which was monitored by PXRD. This phase transition was irreversible when the pressure was released，generating a new pure-silica material ITQ-50（IFY）［22］. The crystallographic struc⁃ture of ITQ-50 was solved and refined by utilizing the PXRD data. ITQ-29 has three different composite building units（CBUs），α-cage（lta），sodalite（sod），and double-four ring（d4r）. During the phase transforma⁃tion of ITQ-29 under the high pressure，only one half of the originald4rcages presented in ITQ-29 remained and the other half break one edge of thed4rcages converting intostiCBUs［Fig.5（A）］. Thesodcages remained intact during the transition process. The originalα-cage will transform to the finalifycavity asproposed in Fig.5（A）. Therefore，a completely new pure-silica ITQ-50 was obtained from ITQ-29. As shown in Fig.5（B），from the topology point of view，round and elliptical 8-ring pore openings along［110］and［001］directions can be identified，generating a 3D channel system. However，from the adsorption point of view，it is a 2D channel system since the elliptical 8-ring pore openings（0.26 nm×0.26 nm）is much smaller than the normal molecular cross section（＞0.34 nm）.

Table 1 Eighty-five novel zeolites discovered since 2007

Fig.5 CBUs of ITQ⁃29(d4r, sod, and lta) and ITQ⁃50(d4r, sti, sod, and ify)(A) and different 8⁃ring channels of ITQ⁃50 viewed along[110]and[001]directions(B)

3.2 Aluminosilicate Zeolites Synthesized in the Excess Fluoride System

Fig.6 Building layer(pst⁃21 layer) nonjointly comprising bre CBUs(A); PST⁃21 and PST⁃22 structures viewed along the c⁃axis(B);the building layer(bre_L1 layer)nonjointly comprising bre CBUs are stacked PST⁃30 structure with 8⁃ring and 10⁃ring channels viewed along the c⁃and a⁃axis(C)

Under excess fluoride conditions where the F―concentration is higher than that of the OSDA，two novel high-silica zeolites PST-21（PWO）and PST-22（PWW）were synthesized by using 1，2，3-trimethylimidazoli⁃um（123TMI+）and 1，3，4-trimethylimidazolium（134TMI+）or 1，2，3，4-tetramethylimidazolium（1234TMI+）ions as OSDAs，respectively［8］. Both PST-21 and PST-22 structures were solved from synchrotron PXRD data and their structural models were further refined against synchrotron PXRD as well. It reveals both structures are built from a new building layer（namedpst⁃21）constructed frombre（［42.54］）units directly［Fig.6（A）］.Furthermore，thepst⁃21layers are stacked along thea-axis through the linkage between the T atoms in the sequencesAAAA…andAAtAAt…to form the PST-21 and PST-22 structures［Fig.6（B）］，respectively. TheAtlayer is obtained by translating 0.5band 0.5cfrom layerA. PST-21 is the first aluminosilicate zeolite with a 2D pore system consisting of mutually intersecting 9-ring channels only. PST-22 also possesses a 2D channel system containing sinusoidal 10-ring channels interconnected by 8-ring pores. Since thebreCBUs are considered as the common building blocks of both structures，another ten chemically feasible hypothetical zeolite structures were built based on the different arrangement ofbreCBUs. Then stabilization energies of multiple methyl-substituted imidazolium derivatives in PST-21，PST-22，and ten hypothetical frameworks were calcu⁃lated and compared. It turned out that 13DMP-C42+could stabilized one of pre-established hypothetical frame⁃works and was further utilized to achieve the targeted synthesis in the condition of excess fluoride，named PST-30（PTY）［24］. The actual structure determination of PST-30 is achieved through PXRD data. In PST-30，thebre_L1layers are stacked along theb-axis without applying any interlayer symmetry operation，forming a 2D channel system consisting of 8-ring channels interconnected by 10-ring channels［Fig.6（C）］.

3.3 Members of RHO Family of Embedded Isoreticular Aluminosilicate Zeolites

ZSM-25，first reported 30 years ago，was synthesized by using Na+and tetraethylammonium（TEA+）ions as SDAs，but its structure remained a mystery for a long time. Until 2015，its structure has been solved from 3D RED data by using a novel phasing method called strong reflections approach and further refined against synchrotron PXRD data. ZSM-25（MWF）can be considered as an expanded version of the knownPAUtopolo⁃gy. Both are built by seven different cage types：lta，d8r，pau，t⁃plg，t⁃oto，t⁃gsm，andt⁃phi. Considering body-centered structures，two interpenetrating cubic scaffolds are identified inPAUand ZSM-25，showing the sequence connected by 8-rings oflta-d8r-pau-d8r-pau-d8r-ltaforPAUandlta-d8r-pau-d8r-pau-d8r-pau-d8rltafor ZSM-25 along each unit-cell edge. And the space between two scaffolds is filled by the other four types of cages. According to the arrangement rules of these cages inPAUand ZSM-25，a series of energetically fea⁃sible hypothetical structures have been predicted by utilizing the strong reflection approach in reciprocal space or the fragment replacement in real space［9］. It is of interest to note that the simplest structure is knownRHOframework and the others can be considered as its expansion version. Therefore，we call this series of struc⁃tures theRHOfamily and structures listed in Fig. 7 are denoted as RHO-G1 to RHO-G8. More importantly，Honget al.［17，25］has successfully synthesized these predicted hypothetical structures［PST-29（RHO-G2）（PWN），PST-20（RHO-G5），PST-25（RHO-G6），PST-26（RHO-G7），and PST-28（RHO-G8）］.

Fig.7 Framework representations of cross⁃sections of RHO⁃G1 to RHO⁃G8 in the RHO family

3.4 EMM-26(EWS)Borosilicate

The borosilicate EMM-26 was synthesized by using 1，6-bis（N-methylpyrrolidinium）hexane as OSDA in the fluoride media［10］. Its structure was solved from RED data and refined against synchrotron PXRD data.EMM-26 can be considered as the assembly of condense layers containingferandmoras CUBs through a mirror symmetry，generating a 2D tortuous 10×10-ring channel system［Fig. 8（A），（B）］. The OSDA was occluded in the cavity as shown in Fig. 8（C）. It is of significance to point out that it is the first time to locate boron-rich T sites from electron diffraction data，which is consistent with the Rietveld refinement results.After removing OSDAs，the proton-form EMM-26 displays a good CO2uptake and CO2/CH4selectivity.

Fig.8 Condense layer of EMM⁃26(A); 3D framework generated by connecting the adjacent layers, which are related by a mirror perpendicular to the a⁃axis(B)and location of the OSDA in the cavity of EMM⁃26(C)

3.5 SCM⁃14(SOR)and SCM⁃15(SOV)Germanosilicates

Germanosilicates SCM-14（SOR）and SCM-15（SOV）from China Petrochemical Corporation could be synthesized by using 4-pyrrolidinopyridine as OSDA in the fluorine medium，but their gel molar compositions are different［20，21］. Both structures were solved from RED and cRED data and then refined against PXRD data.In SCM-14，theac-plane built bymtwandd4rCBUs is further linked by a mirror symmetry，generating a 3D 12×8×8-ring channel system［Fig.9（A），（B）］. It is of interest to note that its projection along thec-axis re⁃semblesMOR-type framework along thec-axis. In SCM-15，stf，lau，mor，andmtwCUBs are identified in theac-plane，which are connected byd4rsalong theb-axis to construct the first 3D 12×12×10-ring channel system［Fig.9（C），（D）］.

Fig.9 ac⁃plane of SCM⁃14(A),3D framework of SOR(B), ac⁃plane of SCM⁃15(C)and 3D framework of SOV(D)

4 Summary and Perspective

In this review，we first introduce conventional and emerging techniques related to X-ray and electron crystallography for zeolite structural characterizations. SXRD，PXRD，3D electron diffraction，HRTEM imaging，HAADF imaging，and iDPC imaging are considered as powerful approaches for unraveling the struc⁃tural information of zeolites through reciprocal space and real space. Secondly，considering their composition，synthetic methodologies used，structure determination approaches，and structural characteristics，we summa⁃rize and categorize 85 novel zeolites discovered since 2007. We select the pure-silica zeolite ITQ-50，several aluminosilicate zeolites（PST-21，PST-22，PST-30，and members ofRHOfamily），borosilicate EMM-26，germanosilicate SCM-14 and SCM-15 as examples for detailed illustrations. The summary and description of zeolite structural characterization methods and these characteristic zeolites may provide some conceptions for the synthesis and structural research of novel crystalline porous materials in the future.

This paper is supported by the National Natural Science Foundation of China（Nos. 21972136，21676262，21991091），the Pioneer Hundred Talents Program，Chinese Academy of Sciences（No.Y706071202），the Dalian National Laboratory for Clean Energy Cooperation Fund，Chinese Academy of Sciences（No. DNL201908），the Key Research Program of Frontier Sciences，Chinese Academy of Sciences（No. QYZDB-SSW-JSC040），VR（Swedish Research Council）Starting Grant（No. 2017-05333）and the Collaboration in the Framework of China-French Joint Laboratory“Zeolites”.