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. 2026 Aug 1;11(31):46595–46602. doi: 10.1021/acsomega.6c04261

High-Throughput Inkjet-Printing Synthesis and Screening of Multicomponent Metallic Oxides for Rapid Decontamination of Chemical Warfare Agent Simulants

Xingqi Huang †, Xuan Guo †,‡, Haibo Wang †,*, Chonglin Zhao †,*
PMCID: PMC13470821  PMID: 42597952

Abstract

Multicomponent metallic oxides exhibit excellent adsorption properties and extensive reactivity toward hazardous chemicals, for which they can be potentially utilized as decontaminants. Understanding the structure–activity relationship between the structural composition of metal oxides and their degradation activity toward chemical warfare agents (CWAs) is crucial for designing new and efficient decontaminants. However, the bottleneck is that metal oxides tend to have low screening efficiency and a long research and development cycle. In this paper, DFT calculations are used to analyze the adsorption and activation capabilities of different metal sites toward typical CWAs, and metal element combinations with potentially high activity are screened out. Based on the computational results, inkjet printing-assisted synthesis with thin-layer chromatography techniques is innovatively applied to the rapid synthesis and screening of CeZrFeO x catalysts’ ternary system, achieving immediate analysis of the degradation activity of different components. Gas chromatography analysis is further employed to verify the reliability of the method. The prepared Ce1Zr0.95Fe0.88O x achieved degradation rates of 99.9% for 2-chloroethyl ethyl sulfide within 12 h. This high-throughput platform has shortened the research and development cycle of decontamination materials by 98%, providing a reference example for the rapid screening and development of new decontamination materials.

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1. Introduction

Hazardous chemical warfare agents (CWAs) are generally highly toxic and easily prepared, making them prime targets in chemical defense. , The pervasive threat of hazardous chemicals, in both industrial accidents and conflict zones, necessitates the development of highly efficient decontamination technologies. Sustainable environmental development policies have established stringent requirements for pollutant degradation technologies and processes. In this context, multicomponent metallic oxides (e.g., Ce-, Zr-, Fe-based oxides) have garnered significant attention due to their tunable redox properties and superior adsorption capacity, and demonstrated reactivity against a broad spectrum of hazardous pollutants. − Despite their considerable promise, the development and optimization of such multicomponent catalysts are notoriously slow and inefficient. The conventional trial-and-error paradigm, which involves sequential synthesis, characterization, and testing of individual compositions, is inherently low-throughput. Furthermore, conventional methods, such as homogeneous hydrolysis and coprecipitation, make it difficult to precisely control the proportion of components in a multicomponent nanoparticulate system, thereby limiting the precise preparation of a multicomponent metal oxide and ultimately affecting its optimal performance. As a result, the research and development cycle can span from months to years, creating a significant bottleneck that impedes the rapid deployment of advanced decontaminants.

To break this paradigm, the field urgently requires innovative methodologies that enable the rapid synthesis and high-throughput screening (HTS) of catalyst libraries. − High-throughput synthesis of inorganic catalysts involves the production of thousands of samples daily using up to four ingredients through thin-film deposition and solution-based methods. An inkjet printing-assisted synthesis (IJP-A) system has become a widely adopted technique for high-throughput fabrication of nanomaterials. , With the capacity to generate 1,000,000 formulations per hour, the system can accurately create mesostructured metal oxide catalysts with multiple components. Furthermore, it allows for precise control and replication of homogeneous atomic compositions at the nanoparticle level within the mesostructure. The chemistry employed in the inkjet mesostructure synthesis process, along with the annealing temperature chosen for creating the test library, can influence the nanoparticle size within the mesostructured walls. Thin-layer chromatography (TLC) is a conventional chromatographic analytical method with a broad spectrum of applications and user-friendly characteristics. In contrast to other chromatographic separation methods, TLC offers numerous advantages. It can perform simultaneous analyses of multiple samples and is straightforward to operate, cost-effective, and environmentally friendly. ,

Herein, we calculated the binding energy of common metal oxides to mustard gas and selected high-activity metal element combinations. To achieve systematic regulation of the components of multicomponent metal oxides, a logarithmic fraction method was employed. Based on this concept, an innovative integrated strategy aimed at establishing a high-throughput synthesis and screening platform for the rapid optimization of multicomponent metal oxides for the degradation of CWAs was developed. It integrated inkjet printing-assisted synthesis with TLC serving as a swift performance evaluation tool. Finally, a ternary metal oxide combination was obtained, and the final composition was determined.

2. Materials and Methods

2.1. Inkjet Printing-Assisted Synthesis of CeZrFeO x

IJP-A was accomplished through the C2Fast-II high-throughput synthesis system manufactured by Hangzhou Nanonov Inc. (Figure S1). For the CeZrFeO x library, three types of metal precursor inks were developed separately. The metal precursor inks developed in this investigation are nontoxic and noncorrosive. All the printing ink properties are listed in Table S1, and the detailed procedure of the IJP-A experiments is displayed in Text S1. After completing the printing process, the samples on the quantitative filter papers were placed in a 60 °C oven and allowed to age for 12 h. Subsequently, the samples were subjected to calcination in the presence of air for 4 h at 450 °C (with a ramp rate of 2 °C per minute) to remove any residual fibers. The metal salts and organic metal compounds in the ink serve as precursors, which are converted into nanometal oxides in situ after being calcined at 450 °C. Various physical characterizations were performed on the 64 different oxide compositions.

2.2. Thin-Layer Chromatography Experiments

TLC is used in this study to optimize the CeZrFeO x samples, which are decontaminants for CWA simulants, such as 2-chloroethyl ethyl sulfide (2-CEES) and dimethyl methylphosphonate (DMMP). TLC, in reality, is a semiquantitative analysis approach that uses established migration distances and concentrations of standard chemicals to conduct qualitative and semiquantitative research. The specific eluents and analytical methods are illustrated in Text S2.

2.3. Characterization

The morphological microstructure and composition of the synthesized samples were observed by transmission electron microscopy (TEM, JEOL JEM-F200, Japan). X-ray energy-dispersive spectroscopy (EDS, Smartedx) was utilized to characterize the composition and distribution of the elements. The crystal structure was ascertained by using an X-ray diffractometer (XRD, Rigaku Ultima IV, Japan) with Cu Kα radiation. The scanning speed was set at 5°/min, and the scanning 2θ range was 5–90°. The Brunauer–Emmett–Teller (BET) surface area and porosity were analyzed using an ASAP 2460 physical adsorption instrument (Micromeritics). X-ray photoelectron spectroscopy (XPS, Thermo Scientific K-α) detected the elemental composition and chemical states using C 1s (284.8 eV) as the standard for energy calibration. Residual 2-CEES was analyzed using a gas chromatography sulfur phosphorus detector (GC-FPD). Intermediate products of 2-CEES were detected by GC–mass spectrometry (GC–MS) (Thermo Scientific Trace 1300 GC system coupled with ISQ 7000 detector, Germany).

3. Results and Discussion

3.1. Selection of Metal Source Particles

According to previous studies, metal oxides with good adsorption and degradation functions for CWAs, such as CeO2, ZrO2, MnO2, TiO2, and Fe2O3, are selected for density functional theory (DFT) calculations. − Sulfur mustard (HD, 2,2′-dichloroethyl sulfide), known as the “king of CWAs”, is elected as the target substance. Further details of the DFT calculations are provided in Text S3. The geometric structure of HD is optimized using the GaussianView software, and the corresponding optimized structure is shown in Figure S2a. The optimization results indicated that the main bond lengths (BL) are BLC–S = 1.843 Å, BLC–C = 1.518 Å, and BLC–Cl = 1.818 Å. At the same time, the electrostatic potential (ESP-Gasteiger) of the HD molecule was calculated using the IQmol graphical interface and is displayed in Figure S2b. It can be seen that for the HD molecule, the S and Cl atoms are rich in negative charges, while the C and H atoms are rich in positive charges. To some extent, this indicates that the S and Cl ends are prone to combining with positively charged groups, while the C and H ends are prone to combining with negatively charged groups.

Through computational simulations of different types of metal materials, the relationship between the structure of the materials and their adsorption performance is analyzed, and the types of metal particles with high adsorption activity for the target pollutants are predicted. Six types of two-dimensional interface crystal structures (Figure S3) and the HD/material interface structure models (Figure S4) were constructed. The HD molecules undergo chemical adsorption at the material interfaces, and the chlorine atoms in the HD bond with the oxygen atoms or metal atoms at the material interfaces. Among them, the (001) crystal plane of CeO2 and ZrO2 is the oxygen atom layer, so the main combination is HD with oxygen atoms. For TiO2, MnO2, and Fe2O3, there are metal centers, and the chlorine atoms in HD are rich in electrons, so the interaction between mustard gas molecules and the metal atoms at the material interface is considered. Most notably, the two-dimensional Zr­(OH)4 material interface mainly contains OH groups, so the possible hydrogen bond interaction of OH···Cl is considered. The optimized structure and corresponding binding energy are shown in Figure . The interaction energy between the material interface and HD molecules is as follows: CeO2(001) > ZrO2(001) > Fe2O3(001) > MnO2(001) > TiO2(001) > Zr­(OH)4(001), which are 3.97, 2.46, 2.13, 1.92, 1.32, and 0.91 eV, respectively.

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Optimized structures of sulfur mustard/material interfaces and the binding energies. a. CeO2 (001), b. ZrO2 (001), c. MnO2 (001), d. TiO2 (001), e. Fe2O3(001), f. Zr­(OH)4 (001).

Single-element metal oxides were prepared through the IJP-A method, and their degradation performances toward 2-CEES, the simulant of HD, were tested. As displayed in Figure S5, the results indicated that they were consistent with the calculation results. Among them, the degradation rates of CeO2, ZrO2, and Fe2O3 toward 2-CEES within 4 h reached 83.79%, 78.90%, and 75.29%, respectively. As a result, we selected cerium–zirconium–iron as the optimal combination for the ternary metal oxide.

3.2. High-Throughput Synthesis and Screening of CeZrFeO x Materials

IJP-A was used to synthesize CeZrFeO x samples, and the rapid screening was conducted through TLC. IJP-A not only enables the preparation of uniform mesoporous metal oxides but also allows for flexible and precise adjustment of the metal element composition of the multicomponent metal oxides. The final composition of the printed materials is determined by the covered area ratio (denoted as CAR). The working curves are influenced by inherent attributes of the inks, such as particle size, viscosity, and surface tension. Figure demonstrates the working curves between the CAR values in CeZrFeO x libraries and the molar ratios of M/Ce (M = Zr, Fe). Here, the CAR value was determined through a computer design program by adjusting the CMY parameter values of different images, while the molar ratios of M/Ce were confirmed by inductively coupled plasma-mass spectrometry (ICP-MS). For this group, CARFe/Ce is equal to 0.33, and CARZr/Ce is equal to 1. The working curves revealed that IJP-A synthesis can provide precise and flexible control of the metal composition within the Ce–Zr–Fe ternary libraries.

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(a) The CMYK parameter values designed through computer software. (b) The working curves between the CAR values and the molar ratios of M/Ce (M = Zr, Fe).

The prepared materials were tested for degradation rate toward 2-CEES using TLC. The TLC method was utilized to efficiently optimize the composition of CeZrFeO x , establishing a direct relationship between the optimization findings and the screening space. The optimized process begins by dividing the selected space into eight subspaces using the bisection method. Each subspace contains 64 distinct chemical formulas comprising different elemental ratios. In the process of quantitative analysis of TLC, the known migration distance and concentration of standard substances are used as a reference to conduct a qualitative and quantitative assessment of the components at the migration end point of each sample. , For 2-CEES, potassium permanganate was selected as the color-developing agent, and different concentrations of standard solution were absorbed in the range of 0.001–0.025 μg/mL (Figure S6). The reference solution was sprayed onto the same thin-layer plate using a glass-point capillary, and the derivative reaction, thin-layer separation, and final quantitative analysis were conducted under optimal conditions. For DMMP, phosphomolybdic acid was selected as the color-developing agent, and different concentrations of standard solution were absorbed in the range of 0.004–0.025 μg/mL (Figure S7). Combined with the IJP-A high-throughput preparation method, the degradation effects of 64 materials toward 2-CEES (Figure ) and DMMP (Figure S8) in a group can be rapidly evaluated within a short period of time.

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TLC screening of CeZrFeO x samples toward 2-CEES.

Although high-throughput experiments do allow for the acceleration of experiments, this does not mean that they can be used for unplanned screening. Optimizing the experimental design for the metal oxide library is extremely important for the high-throughput screening of target materials. In this study, degradation performance analyses were first conducted on several sets of data generated in each iteration. Then, the data with poor performance were eliminated, and further, the optimal data were refined for the next iteration. Eventually, an optimal material library was screened out. This approach avoids the full-space search and reduces the complexity of the screening process, thus saving a significant amount of time.

The IJP-A method and GC analysis were further employed to verify the reliability of the high-throughput synthesis and screening method. During the first round of screening, eight different metal oxide libraries were tested to evaluate the degradation rates of two simulants over a period of 4 h. Figure exhibits eight groups of images containing 64 different small color blocks that were synthesized through the first round of IJP-A. Each specific small color block represents the composition of a multicomponent metal oxide. The degradation results of each group of materials represent the integration of the degradation rates of 64 different compositions of materials within the entire group. The results of the materials prepared according to the first-round group strategy toward 2-CEES are shown in Figure . The G8 material manifested the best performance as the degradation rate of 2-CEES reached 86.39%. Therefore, the G8 material was selected as the base for the next round of screening for further improvement.

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8 groups of materials synthesized through the first round of IJP-A and their degradation performance toward 2-CEES.

During the second round of screening, the screening space was narrowed to the range of the composition variation space, where G8 was located. It evolved and developed into a new set of eight materials (G8-1, G8-2, G8-3, G8-4, G8-5, G8-6, G8-7, and G8-8). These materials displayed a trend of improved degradation effects compared to the first round, proving that the search for the optimal catalyst is gradually underway (Table ).

1. Degradation Rates of 2-CEES and DMMP Reactions within 4 h with the Screening Materials.

Screening round Sample number Ce–Zr–Fe Degradation rate of 2-CEES (%) Degradation rate of DMMP (%)
1# G-1 (0–100), (0–100), (0–100) 82.35 67.89
G-2 (100–200), (0–100), (0–100) 79.05 65.32
G-3 (0–100), (0–100), (100–200) 78.45 60.24
G-4 (100–200), (0–100), (100–200) 76.84 62.78
G-5 (0–100), (100–200), (0–100) 72.94 68.43
G-6 (100–200), (100–200), (0–100) 75.54 68.66
G-7 (0–100), (100–200), (100–200) 76.32 65.94
G-8 (100–200), (100–200), (100–200) 86.39 69.45
2# G-8-1 (100–150), (100–150), (100–150) 83.66 68.65
G-8-2 (150–200), (100–150), (100–150) 80.64 67.89
G-8-3 (100–150), (100–150), (150–200) 79.85 68.63
G-8-4 (150–200), (100–150), (150–150) 81.66 66.74
G-8-5 (100–150), (150–200), (100–150) 78.21 68.45
G-8-6 (150–200), (150–200), (100–150) 78.51 69.76
G-8-7 (100–150), (150–200), (150–200) 79.89 68.43
G-8-8 (150–200), (150–200), (150–200) 87.64 70.46
3# G-8-8-1 (150–175), (150–175), (150–175) 85.98 69.48
G-8-8-2 (175–200), (150–175), (150–175) 84.62 68.64
G-8-8-3 (150–175), (150–175), (175–200) 83.89 67.47
G-8-8-4 (175–200), (150–175), (175–200) 84.36 69.85
G-8-8-5 (150–175), (175–200), (150–200) 82.44 66.32
G-8-8-6 (175–200), (175–200), (150–175) 82.65 69.31
G-8-8-7 (150–175), (175–200), (175–200) 83.78 68.75
G-8-8-8 (175–200), (175–200), (175–200) 89.78 70.65
4# G-8-8-8-1 (175–188), (175–188), (175–188) 89.53 70.12
G-8-8-8-2 (188–200), (175–188), (175–188) 85.32 69.25
G-8-8-8-3 (175–188), (175–188), (188–200) 85.22 70.74
G-8-8-8-4 (188–200), (175–188), (188–200) 84.23 70.34
G-8-8-8-5 (175–188), (188–200), (175–188) 86.47 69.57
G-8-8-8-6 (188–200), (188–200), (175–188) 85.29 71.06
G-8-8-8-7 (175–188), (188–200), (188–200) 87.63 70.53
G-8-8-8-8 (188–200), (188–200), (188–200) 90.71 71.32
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In the third round of screening, the scope of the screening was further narrowed, and the gap between the composition of the catalysts for screening and optimization was reduced. The degradation rates of 2-CEES by all eight oxide libraries reached over 80%. Among them, the G-8-8-8 material exhibited the best performance, and the degradation rate approached 90%, indicating that the optimal catalyst has been discovered and exists in G-8-8-8. The average composition was detected through ICP-MS as Ce1.00Zr0.92Fe0.88O x . This measurement result was very close to the calculated result in the IJP-A as Ce1.00Zr0.88–0.96Fe0.85–0.92O x , further proving the precise control of the printing composition achieved through inkjet printing of metal oxides.

The entire process of material screening is a step-by-step optimization process. The entire catalyst area is screened, but only 1.56% of the composition space is tested. By conducting 32 sets of catalytic experiments for 2048 different catalyst compositions, the number of screening and testing experiments can be significantly reduced.

3.3. Characterization of CeZrFeO x

To explore the multicomponent coupling mechanism between the microstructure and performance of CeZrFeO x material, the structure of the ternary mesoporous metal oxide was characterized. The XRD patterns of CeZrFeO x , CeO2, ZrO2, and Fe2O3 are shown in Figure S9.The XRD pattern for the CeZrFeO x group was obtained during calcination at 450 °C, and the diffraction peaks of the as-prepared compounds were associated with the fluorite structure of CeO2 (JCPDS 00-034-0394). , No impurity diffraction peaks were detected, indicating the incorporation of Zr and Fe ions into the CeO2 lattice. As the amount of Ce decreased, the diffraction peaks gradually shifted to higher angles due to the reduced interplanar spacing and unit cell parameters, resulting from the isomorphous substitution of larger Ce4+ ions (ionic radius is 0.097 nm) with smaller Zr4+ (ionic radius is 0.084 nm) and Fe3+ (ionic radius is 0.093 nm).

Figure exhibits the transmission electron microscopy (TEM) images and energy spectra of the Ce1.00Zr0.92Fe0.88O x . It is observed that the distributions of iron, zirconium, and cerium elements coincide and are concentrated within the metal oxide region, indicating the uniformity of the metal oxide library produced through IJP-A. As shown in Figure S10, the representative low-magnification scanning electron microscopy (SEM) images and the corresponding element distribution maps of Ce, Zr, and Fe confirm the component uniformity of the material on a macroscopic scale. The degradation performance is mainly dependent on the reaction selectivity of the metal particles and the mass transfer effect of the system. Different metal materials have anisotropic properties on each crystal plane, and the atomic arrangement, bonding mode, surface defects, etc., are all different. Therefore, different components of nanometal oxide materials show significant differences in interface composition and surface interfacial energy. Fe3+, Zr4+, and Ce4+ have similar atomic ratios and are more likely to enter the CeO2 lattice, causing lattice distortion and generating more defects, vacancies, etc., which are the active centers of the degradation reaction. As shown in Figure S11, by means of adjusting the proportion of components, the lattice arrangement of the metal oxide undergoes significant changes, indicating that changing the composition of the metal oxide can significantly improve its degradation performance. Therefore, it is very important to explore and develop high-throughput preparation and screening technologies for multimetal oxide materials.

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TEM images and elemental mapping of CeZrFeO x .

The N2 isothermal adsorption–desorption curves of the CeZrFeO x samples are displayed in Figure S12. The curves of all samples exhibit the characteristic features of a type IV curve, with H3-type hysteresis loops. The appearance of these hysteresis loops indicates the presence of mesoporous structures in the samples. The precursor solution-based ink used in this study is a homogeneous solution formed by dissolving soluble metal salts and organic metal compounds in a solvent. After being printed, deposited, dried, and calcined, this solution could be in situ transformed into metal oxide particles with different compositions and mesoporous structures. The selection can be made arbitrarily, provided that the printed mesostructured wall maintains a consistent atomic arrangement on the nanoscale, typically spanning just a few nanometers. The pore size distribution also affects the degradation performance of metal oxides on CWAs. The relevant pore size distribution chart is shown in Figure S13. As displayed in Table S2, the pore size distribution of CeZrFeO x samples is relatively concentrated, mainly ranging from 2 to 10 nm. The Ce1.00Zr0.92Fe0.88O x sample has a larger specific surface area, which is approximately 163.8 m2/g. The mesoporous structure of decontaminants can ensure that CWAs molecules enter the interior of the decontaminants and does not affect the specific surface area. Therefore, the Ce1.00Zr0.92Fe0.88O x sample demonstrates better adsorption and degrading capabilities toward CWAs.

To further reveal the structure–activity relationship between the lattice arrangement composition and the active centers, such as defects and vacancies, the XPS O 1s spectra of the CeZrFeO x samples were measured, and the results are shown in Figure . The O 1s spectrum can be divided into three peaks, located at 529.0–529.5, 530.5, and 531.5 eV, corresponding to three different types of oxygen (Table S3), namely lattice oxygen (OI), OH– (OII), and adsorbed H2O (OIII). Isolated hydroxyl groups are regarded as the active centers for the degradation of CWAs. Therefore, the amounts of OII and OIII on the surface can be directly correlated with the degradation performance. The contents of OII and OIII in the Ce1Zr0.95Fe0.88O x sample are 35.3% and 13.8%, respectively, which are higher than those of the other two samples. This further demonstrates the effectiveness of the high-throughput screening method.

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O 1s spectrum of CeZrFeO x samples.

3.4. Degradation Performance of Ce1Zr0.95Fe0.88O x

The three-component ratio of Ce1.00Zr0.88–0.96Fe0.85–0.92O x demonstrated the best degradation performance toward the two target substances. Therefore, the Ce1Zr0.95Fe0.88O x composite material was obtained according to the optimal molar ratio. The degradation effects of Ce1Zr0.95Fe0.88O x toward 2-CEES and DMMP were tested, and the results are shown in Figure . During the initial rapid reaction stage, the liquid molecules were rapidly adsorbed and diffused on the material surface, reaching the accessible reactive sites on the surface. Once all these accessible reactive sites were occupied, the surface reaction was restricted and then entered a steady-state slow reaction stage. For 2-CEES, the degradation rate of the ternary composite material within 4 h reached over 90%, and the degradation rate after 12 h could reach over 99.9%, with a half-life of about 30 min. In contrast, the P–O bond of DMMP in the presence of a hydrolytic reaction has greater stability; hence, only 60% degradation was observed in 12 h. However, the degradation rate reached 99.9% within 24 h.

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Degradation kinetics of (a) 2-CEES and (b) DMMP by Ce1.00Zr0.95Fe0.88O x .

4. Conclusion

The optimal combination of ternary metal elements was screened by DFT calculations. For the first time, high-throughput synthesis and screening based on the IJP-A method and TLC have been successfully introduced into the development of a series of CeZrFeO x decontaminants. The strategy designed in this study is simple and feasible, and the number of material preparations was significantly reduced. Furthermore, the entire library was inspected, resulting in a significant reduction in the number of validation tests. Following the optimization of experimental parameters, the degradation rate of 2-CEES by the best Ce1.00Zr0.95Fe0.88O x material reached 99.9% in 12 h. Although the initial degradation was relatively slow, the degradation rate of DMMP within 24 h could still reach 99.9%, demonstrating that this material also has complete degradation ability for nerve agents. The composition adjusted through TLC inspection was duplicated and validated via manual preparation. More importantly, the materials with good performance obtained through TLC screening were verified by GC, demonstrating the feasibility of this method. It is anticipated that the complementary application of IJP-A and TLC will be used to discover functional materials in other fields.

Supplementary Material

ao6c04261_si_001.pdf (982.6KB, pdf)

Acknowledgments

This study was supported by the State Key Laboratory of NBC Protection for Civilian (SKLNBC2022-05).

The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acsomega.6c04261.

  • The detailed approach for calculations and experiments, as well as some results of interest (PDF)

The authors declare no competing financial interest.

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