Steam-assisted Crystallization Research Articles

Hydrogenation of CO2 to p-xylene over ZnZrOx/hollow tubular HZSM-5 tandem catalyst

The conversion of CO2 into specific aromatics by modulating the morphology of zeolites is a promising strategy. HZSM-5 zeolite with hollow tubular morphology is reported. The morphology of zeolite was precisely controlled, and the acid sites on its outer surface were passivated by steam-assisted crystallization method, so that the zeolite exhibits higher aromatic selectivity than sheet HZSM-5 zeolite and greater p-xylene selectivity than chain HZSM-5 zeolite. The tandem catalyst was formed by combining hollow tubular HZSM-5 zeolites with ZnZrOx metal oxides. The para-selectivity of p-xylene reached 76.2% at reaction temperature of 320 °C, pressure of 3.0 MPa, and a flow rate of 2400 mL g−1 h−1 with an H2/CO2 molar ratio of 3/1. Further research indicates that the high selectivity of p-xylene is due to the pore structure of hollow tubular HZSM-5 zeolite, which is conducive to the formation of p-xylene. Moreover, the passivation of the acid site located on the outer surface of zeolite effectively prevents the isomerization of p-xylene. The reaction mechanism of CO2 hydrogenation over the tandem catalyst was investigated using in-situ diffuse reflectance Fourier transform infrared spectroscopy and density functional theory. The results showed that the CO2 to p-xylene followed a methanol-mediated route over ZnZrOx/hollow tubular HZSM-5 tandem catalysts. In addition, the catalyst showed no significant deactivation in the 100 h stability test. This present study provides an effective strategy for the design of catalysts aimed at selectively preparing aromatics through CO2 hydrogenation.

Spherical Binderless 4A/5A Zeolite Assemblies: Synthesis, Characterization, and Adsorbent Applications.

Zeolite microspheres have been successfully applied in commercial-scale separators such as oxygen concentrators. However, further enhancement of their applications is hampered by the post-synthetic shaping process that formulates the zeolite powder into packing-sized spherical bodies with various binders leading to active site blockage and suboptimal performance. Herein, binderless zeolite microspheres with a tunable broad size range from 2 µm to 500 µm have been developed with high crystallinity, sphericity over 92%, monodispersity with a coefficient of variation (CV) less than 5%, and hierarchical pore architecture. Combining precursor impregnation and steam-assisted crystallization (SAC), mesoporous silica microspheres with a wide size range could be successfully transformed into zeolite. For preserved size and spherical morphology, a judicious selection of the synthesis conditions is crucial to ensure a pure phase, high crystallinity, and hierarchical architecture. For the sub-2-µm zeolite microsphere, low-temperature prolonged aging was important so as to suppress external zeolization that led to a large, single macroporous crystal. For the large 500 µm sphere, ultrasound pretreatment and vacuum impregnation were crucial and facilitated spatially uniform gel matrix dispersion and homogenous crystallization. The obtained zeolite 5A microspheres exhibited excellent air separation performance, while the 4A microspheres displayed ammonium removal capabilities. This work provides a general strategy to overcome the existing limitations in fabricating binder-free technical bodies of zeolites for various applications.

Synthesis of a hierarchical TS-1 zeolite with tunable macropore size and its performance in the catalytic oxidation reactions

Hierarchical TS-1 zeolites with tunable macropore size were synthesized based on a steam-assisted crystallization strategy, which exhibited excellent activity in the catalytic oxidation reactions.

In-Situ Growth of Embryonic TS-1 on Amorphous Silica via Steam-Assisted Crystallization: Correlation of Structural Properties and Catalytic Performance of Embryonic, Crystalline, and Amorphous Titanosilicate Catalysts

In-situ growth of supported embryonic TS-1 zeolite (<10 nm) on a silica support was achieved by steam-assisted crystallization (SAC). The use of low amounts of TPABr and steam at a moderate temperature of 130 °C was the key factor to control partial transformation of silica into supported embryonic TS-1. Compared with the reference crystalline TS-1, supported embryonic TS-1 exhibits a higher activity in dibenzothiophene (DBT) oxidation (TOF: 8–275 h–1 vs 2.7–160 h–1 at 30–98 °C), a higher resistance to poisoning by nitrogen-containing compounds, and a higher selectivity (>97%) in the productive utilization of the oxidant in DBT oxidation. The activity of the amorphous titanosilicate (TOF: 21.2–210 h–1 at 30–80 °C), the solid precursor of the SAC process, was higher than that of the embryonic and the crystalline TS-1. The analysis of the structural properties–catalytic performance of these catalysts showed an improved accessibility to defective Ti active sites “Ti(OH)(OSi)3” with higher catalytic activity. The results of this study should be encouraging to unearth many other active amorphous catalysts with the potential of industrial application.

MFI Type Zeolite Aggregates with Nanosized Particles via a Combination of Spray Drying and Steam-Assisted Crystallization (SAC) Techniques

Hydrothermal synthesis is the state-of-the-art technique for the preparation of zeolites and related porous solids. However, when it comes to the preparation of nanosized zeolites, this technique is limited by low yields, separation problems and high amounts of waste. In this work, we utilized the strengths of a combination of spray drying and steam-assisted crystallization (SAC), also known as dry gel conversion, to reduce these problems. At spray drying temperatures between 300 and 400 °C, it was possible to convert all the amorphous material via SAC into zeolite particles without extra addition of template. Kinetic studies of SAC revealed that about 4 to 8 days are needed to achieve the formation of a 100% crystalline product. The newly formed crystalline phase was crystallized on the surface of the nanosized zeolites and led to a slight increase in the primary particle size while the macroscopic morphology of the spray-dried aggregates was preserved. This work demonstrates that the combination of spray drying and SAC are useful tools in supplementing the hydrothermal synthesis of nanosized zeolites.

Effect of SiO2/Al2O3 ratio on the electrochemical performance of amorphous zeolite loaded with cobalt oxide grown via steam-assisted crystallization method.

Improving the performance of a supercapacitor is one of the main approaches to solve the energy shortage problem. Electrode material is one of the key components limiting the efficiency of a supercapacitor. Discovering, tuning, and improving electrode materials are very important. This work reports the effect of SiO2/Al2O3 ratio on electrochemical performances of amorphous zeolites ZSM5 (AZ) and H-ZSM5 (H-AZ) loaded with cobalt oxide. Two SiO2/Al2O3 ratios (1 = 6.2 and 2 = 8.3) of AZ1, AZ2 and H-AZ1, H-AZ2 were synthesized by a facile impregnation method. Then, controlled masses of cobalt oxide were introduced to enhance the supercapacitive performances of the amorphous zeolite. Investigation of the SiO2/Al2O3 ratio in the cobalt oxide/zeolite composite (Co/AZ and Co/H-AZ) was carried out to unveil its effect on the electrochemical properties. Worthy of note is the fact that the resulting electrode materials exhibited supercapacitive behavior that is effective over a potential window ranging from 0 to 0.5 V in potassium hydroxide (1 M KOH) aqueous electrolyte. Results from Galvanometry Charging and Discharging (GCD) analyses show that the modified Ni-foam electrodes loaded with Co/H-AZ1 and Co/H-AZ2 are capable of delivering a relatively high specific capacity from 45.97 mA h g-1 to a high value of 72.5 mA h g-1 at 1 A g-1 and Ni-foam electrodes loaded with Co/AZ1 and Co/AZ2 exhibited values from 26 mA h g-1 to 52.83 mA h g-1 respectively. It is clearly shown that, when the mass ratio SiO2/Al2O3 increases, the specific capacity increases as well. It was also noticed that after 2000 cycles, Co/H-AZ1 and Co/AZ1 have a poor coulombic efficiency while Co/H-AZ2 and Co/AZ2 exhibited 98% for coulombic efficiency. Finally, this study shows that to fabricate high performance supercapacitors with amorphous zeolite loaded with cobalt oxide, one should keep the ratio of SiO2/Al2O3 as high as possible during synthesis.

Can We Form Mesoporous Zeolites by Steam Assisted Crystallization of MCM-41?

The possibility of crystallizing silicalite-1 (MFI) from the pore walls of as-synthesized MCM-41 via steam-assisted crystallization (SAC) was thoroughly investigated. A kinetic study was conducted through the impregnation of as-synthesized MCM-41 with the structure-directing agent tetrapropyl-ammonium hydroxide (TPAOH). Materials obtained after different SAC treatment times (1-288 h) were characterized by XRD, nitrogen physisorption at 77 K, TGA/DTA, and SEM. The achieved results allowed us to conclude that during SAC treatment, rapid destruction of the hexagonal mesophase occurs with the enlargement of mesopores, probably by their coalescence, until achieving non-porous amorphous silica. Only thereafter is the crystallization of the MFI phase evidenced through the development of micron-sized (&gt;10 µm) MFI structured crystals. This study suggests the probable practical impossibility of even partial crystallization of the pore walls of mesoporous materials by SAC.

Rapid and Effective Way to Synthesize Highly Crystalline Nanosized SAPO-34 Particles.

SAPO-34 nanocrystals with sizes of 50-150 nm were obtained via steam-assisted crystallization (SAC) for 5 h at 200 °C from two types of aluminum precursors-aluminum isopropoxide and boehmite. A reaction mixture composition with a small amount of organic template tetraehylammonium hydroxide (TEAOH) was used with the molar ratio TEAOH/Al2O3 = 1/1. The alumina precursor type and duration of the SAC (5 and 24 h) on the crystal size, texture, and acid properties were investigated. The SAPO-34 nanocrystals that we obtained possess a large micropore volume of 0.22-0.24 cm3/g and a specific surface area of 651-695 m2/g. When the crystallization was prolonged for up to 24 h, a SAPO-18 structure appeared, but the micropore and mesopore volumes changed insignificantly. Using boehmite as the aluminum precursor led to higher mesoporosity of the material but a little bit lower acidity when compared with the samples prepared from aluminum isopropoxide. In addition, the method proposed was used for preparing a SAPO-34-coated aluminum adsorber heat exchanger. Thus, the synthesis method proposed is affordable and effective to prepare SAPO-34 highly crystalline nanoparticles, with no need for post-synthetic procedures as the mother liquor separation from nanocrystals.

A novel MOFs-induced strategy for preparing anatase-free hierarchical TS-1 zeolite:synthesis routes, growth mechanisms and enhanced catalytic performance

Titanosilicate-1 zeolites (TS-1) as one of the most commonly used catalysts for alkene epoxidation, construction of hierarchical pores as well as elimination of anatase to promote mass transportation and avoid invalid decomposition of hydrogen peroxide are always desirable yet challenging goals. Here, a novel and unique Ti-based metal organic frameworks (MOFs)-induced synthetic strategy for fabricating anatase-free hierarchical TS-1 was first proposed. All the components of MOFs perform different functions: the uniformly distributed Ti nodes replace conventional tetrabutyl titanate (TBOT) to serve as sole Ti source for constructing zeolite crystal; the separated ligands can be embedded in the zeolite framework and act as template to in situ build hierarchical pore structure; the coordination interaction between Ti nodes and ligands can efficiently avoid the anatase generation by balancing the forming rates of Ti-OH and Si-OH. This synthetic strategy is of general applicability, and two different synthetic routes including traditional hydrothermal process and steam assisted crystallization (SAC) procedure are successfully adopted. The obtained hydrothermal TS-1 and SAC anatase-free samples all possess abundant intercrystalline mesopores of 20–50 nm and even macropores between 50 and 150 nm, improving the conversion over 25 % for 1‑hexene epoxidation than TS-1 sample prepared by conventional route. The influences of the amount of Ti MOFs precursor and the crystallization process are studied in detail, and possible synthesis mechanisms are proposed. This MOFs-induced strategy might open up an avenue for the rational design of ideal and hierarchical zeolite to boost the catalytic efficiency.

Co-MOF nanosheet supported on ZSM-5 with an improved catalytic activity for air epoxidation of olefins

A composite material ZSM-5@Co-MOF containing Co-MOF and ZSM-5 was successfully prepared by steam-assisted crystallization of Co-MOF on the zeolite surface. Compared to physically mixing Co-MOF on the zeolite surfaces, Co-MOF nanosheets were uniformly attached to external surfaces of the ZSM-5 crystals because of the enhanced interaction between zeolite and Co-MOF in the composite. In addition, the Co-MOF was distributed as a nanosheet structure, and its dispersibility was greatly enhanced, in which this behavior led to more uniform distribution of the deposited active sites. Interestingly, the designed composite exhibited an excellent catalytic performance for the epoxidation of α-pinene with air. Compared to isolated Co-MOF and ZSM-5, high yield of the product (94.4%) was obtained over the 0.5ZSM-5@Co-MOF-150 composite due to the highly dispersed Co-MOF nanosheet. This opens up interesting prospects for developing new zeolite@MOF composite catalysts as efficient heterogeneous catalysts.

Combining solid state grinding and steam-assisted crystallization for green organotemplate-free synthesis of ZSM-5

Green synthesis of zeolite has been made much progress due to solvent-free grinding methods. Although solid-state synthesis is a simple green process with a high yield, its kinetics of the solid-phase crystallization process is still slow and the precursor materials are not uniformly heated throughout the reactor resulting into the poor uniformity of the particles. Herein, we report a high-efficiency organotemplate-free synthesis of ZSM-5 combining solid state grinding and steam-assisted crystallization. Solid state grinding (SSG) of aluminosilicate precursor avoids usage of solvent and steam-assisted conversion (SAC) in an organic-template-free condition grants a fast crystallization rate of ZSM-5. More importantly, the vapor fulfilled in the reactor ensures uniform heating of solid feedstock for crystallization of ZSM-5, leading the high crystallinity and the uniform particle size distribution. This combination can guarantee 100% relative crystallinity of ZSM-5 in 12 h, compared to that of 80% crystallinity from sole solid state at the same crystallization temperature (180 °C). Furthermore, this combination can achieve 83% relative crystallinity of ZSM-5 at 160 °C, compared to that of 37% crystallinity from the solid state alone. Highly dispersed ZSM-5 zeolite with adjustable SiO2/Al2O3 ratio is prepared by steam-assisted crystallization of grinding solid raw materials. The catalytic activity of ZSM-5 catalyst from this combination strategy for the acetalization of cyclohexanone is superior to that of the solid-state method alone. This sustainable and green synthesis method provides a potential way for the preparation of zeolites in an industrial scale.

Forming of Block Zeolites Using 3D Printing Technology

Zeolite blocks with 10% binder and without binder were formed using 3D printing technology. A polylactide template with the preset shape and structure of channels was printed on a 3D printer. The zeolite material was formed in the voids of this template. Finally, the template was burned out from the final block. Blocks with a binder were prepared by filling the template with a paste containing microcrystalline zeolite of MFI structural type. Blocks without binder were prepared by steam-assisted crystallization leading to the formation of zeolite nanocrystals in the H-form in the template channels. A relatively strong block consisting of MFI-type zeolite and reproducing the polymer template void volume was obtained.

An all-in-one zeolite@Ru–Al2O3 nanoplatform toward highly efficient, anti-coking, and recyclable hydrocarbon cracking catalysis

Efficient utilization of hydrocarbon fuels holds great significance for the current vehicle low-emission requirements and future carbon-neutral society. However, the scenario that limits the effective fuel use and combustion is the present undesirable hydrocarbon-cracking catalysts of low activity, serious coking, and easy degradation. To tackle these issues, we rationally designed and synthesized an active, anti-coking, and recyclable all-in-one zeolite@Ru–Al2O3 catalyst on FeCrAl support by steam-assisted crystallization and atomic layer deposition. Ru nanoclusters dispersedly on ZSM-5 can boost the catalytic efficiency for hydrocarbon cracking and anti-coking, while the protective Al2O3 thin layers further ensure the reusable economy. As for n-dodecane (C12H26) cracking reaction, the ZSM-5@Ru–Al2O3 showed a high unit activity up to 0.1253%·ml·mg−1·min−1, low-carbon deposition rate, and the enhanced first-cycle carbon removal rate of 78.3% for recyclable use. Density functional theory (DFT) calculations have further confirmed that high catalytic efficiency and low-carbon deposition benefit from the timely adsorption of C12H26 and timely transfer of reactant products at the composite interface. This work opens interesting possibilities for the rational design and fabrication of high-efficient, anti-coking, and recyclable hydrocarbon cracking catalysts through multifunctional structural regulations.

Confined space synthesis of Ni(OH)2-impregnated three-dimensional ordered mesoporous carbon as a high-performance supercapacitor electrode

Regulable loading of Ni(OH)2 crystals by using three dimensionally ordered mesoporous carbon (3DOMC) as a support is achieved through a confined growth strategy accompanied by steam-assisted crystallization. Dual forms of high-crystalline nanosheet-like Ni(OH)2 severally distribute within mesopores or over the outer surface of 3DOMC particles depending on the loading amount (3% − 15%) of Ni(OH)2. Benefitted from the highly hybrid combination and efficient electrolyte diffusion, the obtained Ni(OH)2/carbon nanocomposites exhibit an excellent electrochemical performance, and the optimal sample of 6%_Ni(OH)2/3DOMC with confined extra-small Ni(OH)2 nanosheets as dominant shows the highest specific capacitance of 552.5F.g−1 at 1.0A·g−1, which is 330% higher than the contrast sample by using actived carbon as the support. Furthermore, the assembled hybrid supercapacitor by using 6%_Ni(OH)2/3DOMC and 3DOMC as positive and negative electrodes displays an energy density of 11.7 Wh.kg−1 at 288.1 W.kg−1 and a superior charge/discharge stability. It is expected that the flexible component, well-defined structure, and superior electrochemical performance could promote a great application potential of Ni(OH)2/3DOMC nanocomposites as supercapacitor electrodes and in other energy storage devices.

Efficient and clean epoxidation of methyl oleate to epoxidized methyl oleate catalyzed by external surface of TS-1 supported molybdenum catalysts

Methyl oleate (MO) macromolecules are unable to access the microporous channel of conventional titanium silicalite-1 (TS-1) zeolite, which leads to the low catalytic activity of epoxidation of MO. Herein, the small-size TS-1 (TS-1-s) zeolite with a large surface area was synthesized successfully through steam-assisted crystallization, and then a novel blocked TS-1-s supported molybdenum (Mo/TS-1-bs) catalysts were prepared for efficient epoxidation of MO with clean H 2 O 2 to produce epoxidized methyl oleate (EMO). Various characterization results show the introduced Mo species are highly dispersed on the outer surface of TS-1-s without destroying the structure of the MFI type zeolite and the tetrahedral framework titanium (Ti 4+ ). Interestingly, a large number of Mo 6+ species exhibit certain epoxidation activity attributing to the generating of electrophilic molybdenum hydroperoxide (Mo–OOH) species via Mo species combined with H 2 O 2 , which could adsorb and react easily with MO molecules. Furthermore, the Mo species are also coordinated with Ti 4+ species through the O atom resulting in the facile attack of the Ti–O bonds by H 2 O 2 and easy to form an active intermediate. Therefore, compared with the conventional TS-1, the Mo/TS-1-bs shows higher catalytic activity in the epoxidation reaction. However, the acidity of Mo/TS-1-bs catalysts increases with increasing the Mo-loading owing to the formation of Lewis acid, which leads to the side reactions and the decrease of EMO selectivity. As a consequence, the efficient, non-corrosive and green catalytic system for epoxidation of MO was developed, and the activity improvement of Mo species and the influence of acid were also demonstrated. • The clean small-size TS-1 and Mo/TS-1-bs catalysts were prepared successfully for epoxidation of methyl oleate (MO). • Mo species can promote the MO epoxidation through generating of molybdenum hydroperoxide and coordination with Ti 4+ . • The acidity of Mo/TS-1-bs catalysts can decrease the selectivity of epoxidized methyl oleate.

Steam-assisted strategy to fabricate Anatase-free hierarchical titanium Silicalite-1 Single-Crystal for oxidative desulfurization

As an important heterogeneous catalyst, Titanium Silicalite-1 (TS-1) zeolite has been widely applied in various catalytic processes. Here, hierarchical TS-1 single-crystals were successfully synthesized by a steam-assisted crystallization strategy using hierarchically porous titanium-containing silica (Ti-NKM-5) as a precursor. Due to the presence of large mesopores (10–40 nm)， the microporous structure-directing agents penetrated the interstitial structure of silica particles, inducing the dissolution and crystallization process. During crystallization, the generated nanocrystals grew together to form a hierarchical structure. Titanium was fully incorporated into the zeolite framework, and no extra-framework anatase was formed. Compared with the traditional microporous TS-1 zeolite, the synthesized hierarchical TS-1 single-crystal exhibited superior catalytic performance in oxidative desulfurization (ODS) of dibenzothiophene (DBT) and 4, 6-dimethyl dibenzothiophene (4, 6-DMDBT) owing to the hierarchically porous and anatase-free structure. The recycling test revealed the durability of the obtained hierarchical TS-1 catalyst under moderate reaction conditions.

Nanofabrication of Ni-incorporated three-dimensional ordered mesoporous carbon for catalytic methane decomposition

Incorporation of Ni active species with mesoporous carbon and the resulting composite materials have received much attention due to their nature of flexibility derived from a confluence of metallic and carbonic properties and numerous textural advantages inherited from mesoporous carbon substrates, contributing to their versatility in energy transformation. However, the efficient integration of such composite materials with complementary advantages in properties is still highly desired. Herein, confined growth of Ni(OH)2 nanosheets within three dimensionally ordered mesoporous carbon (3DOMC) by steam-assisted crystallization is propose in this paper. High-crystalline Ni(OH)2 species are found in two forms of confined extra-small nanosheets within the mesopores of 3DOMC and staggered nanosheets over the particles of 3DOMC, which can be reduced to the highly segregative Ni nanoparticles by sufficient reduction. By using as a catalyst for methane decomposition to produce COx-free hydrogen, Ni/3DOMC contributes a maximum CH4 conversion of 66.5% and H2 output rate of 7.4 mmol. gcat−1·min−1 at 850 °C, more superior to the conventional Ni-incorporated active carbon (Ni/AC) catalyst. Moreover, the Ni/3DOMC catalyst also exhibits not only a higher initial reaction rate but also an improved catalytic stability attributed to the abundant homodispersed Ni active species by the highly hybrid structure. It is expected that the flexible component, well-defined structure, and superior CMD performance could promote a great application potential of Ni/3DOMC nanocomposites in catalysis.

Steam-assisted crystallization of highly dispersed nanosized hierarchical zeolites from solid raw materials and their catalytic performance in lactide production.

A solvent-free route based on solid raw materials affords higher product yield and lower waste production compared to the traditional hydrothermal synthesis. However, the as-made zeolites usually present blocky aggregation states, limiting their mass transfer and exposure of active sites in catalytic applications. Herein, highly dispersed nanosized hierarchical Beta zeolites with varied Si/Al ratios were prepared via steam-assisted crystallization from ball-milled solid raw materials. Thanks to the sufficient mixing of solid raw materials and favorable migration of solid mixture, nanosized Beta zeolites are obtained that are assembled from nanoparticles (∼15 nm) and possess abundant interconnected intraparticle mesopores. The strategy can also be extended to synthesize nanosized hierarchical ZSM-5 zeolites. The as-prepared Beta zeolite (Si/Al = 10) exhibits outstanding catalytic performance in conversion of lactic acid to lactide (as high as 77.5% in yield). This work provides avenues for simple and cost-efficient synthesis of highly dispersed nanosized hierarchical zeolites, promising their important catalytic applications.

In-situ preparation of hierarchical Beta zeolite by steam- assisted crystallization method using meso-macroporous silica

In this paper, a series of meso-macroporous silica (MMS) were prepared by phase separation, then mic-meso-macroporous Beta zeolite was prepared by steam-assisted crystallization (SAC) method using the meso-macroporous silica as substrate. The factors such as the amount of water, crystallization time, aluminum source, amount of template agent during the SAC method were investigated. Various characterization methods such as BET, XRD, SEM were used to investigate the physical and chemical properties of the prepared materials. The results showed that the meso-macroporous silica could be transformed into Beta zeolite through the SAC method while the macroporous structure was still maintained.

Sandwich Evaporation-Solvent Annealing Fabrication of Highly Crystalline MAPbIxCl3-x Perovskite Solar Cells.

Perovskites doped with chlorine (Cl-), which are usually fabricated using the solution process, can effectively improve the stability and carrier mobility. Compared with the low tolerance of the solution process that relies mostly on personal skill, thermal evaporation is an important method for large-scale production of perovskite solar cells but the production cost is high. In this study, the sandwich evaporation-solvent annealing (SE-SA) method is proposed. Using sandwich evaporation with a low-cost chamber of the sandwich evaporation technique (SET) made in the laboratory and with the help of DMSO steam-assisted crystallization, we have successfully produced chlorine-containing perovskite solar cells with a high crystallinity and a high efficiency of 15.1% with Voc = 0.98 V, Jsc = 21.94 mA/cm2, FF = 74.29%, and Rs = 3.66 Ω·cm2, which can greatly reduce the production cost. It is worth mentioning that all the processes are carried out outside a glove box, which makes it possible for large-scale production of chlorine-containing perovskite solar cells by evaporation.