Efficient Preparation of Black Phosphorus Enabled by Sn₂₄P_19.3I₈/Graphite Catalyst with Enhanced Thermal Conductivity

Tun Nile 1

Hao Sun 1

Tingting Xu 1,3✉ Phone+15606949338 Email15606949338@163.com

Yu Yang 1

Caimei He 2

Wen Chen 1

Peichao Lian 1,3✉ Phone+15969504763 Emaillianpeichao@126.com

1 Faculty of Chemical Engineering Kunming University of Science and Technology 650500 Kunming China

2 Department of Chemical Engineering Tsinghua University 100084 Beijing China

Kunming University of Science and Technology No.727, Jingming South Road Yunnan Chian

Tun Nile ¹, Hao Sun ¹, Tingting Xu ^1*,Yu Yang ¹, Caimei He ² ,

Wen Chen ¹, Peichao Lian ^1*

¹ Faculty of Chemical Engineering, Kunming University of Science and Technology, Kunming 650500, China.

² Department of Chemical Engineering, Tsinghua University, Beijing 100084,China.

Corresponding Author:

1. Tingting Xu

Kunming University of Science and Technology

No.727, Jingming South Road, Yunnan, Chian

Tel: +15606949338

E-mail address: 15606949338@163.com

2.Peichao Lian

Kunming University of Science and Technology

No.727, Jingming South Road, Yunnan, Chian

Tel: +15969504763

E-mail address: lianpeichao@126.com

Abstract

The mineralization method boasts advantages including high product purity, controllable crystal structure and good reproducibility, making it a promising approach for the preparation of black phosphorus (BP). However, the employed Sn₂₄P_19.3I₈ catalyst suffers from pronounced sintering during the preparation process, which severely compromises its catalytic activity and cycle period. The yield (56.0%) was horribly low after two cycles of BP preparation by using Sn₂₄P_19.3I₈. Herein, intrinsically low thermal conductivity was demonstrated to the decreased catalytic performance of Sn₂₄P_19.3I₈ catalyst. To overcome this issue, graphite was integrated with Sn₂₄P_19.3I₈ (Sn₂₄P_19.3I₈/Gra) for improving the thermal conductivity, which effectively alleviated the issue of local heat accumulation and therefore overcame sintering of Sn₂₄P_19.3I₈. As expected, an exceptionally high yield of 83.3% was achieved even after nine cycles of BP preparation based on the Sn₂₄P_19.3I₈/Gra composite catalyst, highlighting the catalytic robustness. This work provided a feasible production of high-quality BP, paving the way for its broad industrial application.

Keywords:

Mineralization

Black phosphorus

Sn₂₄P_19.3I₈/Graphite

catalytic activity

thermal conductivity

1.Introduction

Black phosphorus (BP) is a stable two-dimensional material among the allotropes of phosphorus[1–2]. Benefiting from the integrated unique features of tunable bandgap (0.3-2.0 eV), exceptionally high charge-carrier mobility (~ 1000 cm²/(V·s)), broadband optical absorption (spanning UV to IR) and pronounced in-plane anisotropy[3–5], BP exhibits attractive application potential in high-capacity energy storage batteries[6–7], high-speed nanoelectronics[8–11] ultrasensitive photodetectors[12–13], targeted drug delivery systems and photocatalytic reactions[11–19] Yet, the lack of scalable and effective preparation strategies poses a fundamental bottleneck in the widespread industrial deployment of BP.

Various methods such as high-pressure means[20], mechanical ball milling[21], mercury reflux[22], bismuth melting[23] etc, have been proposed for the BP preparation. However, these methods often display one or more inherent drawbacks of harsh reaction conditions, low yield, poor quality and limited scalability, greatly blocking the large-scale BP production. A breakthrough was achieved by Nilges et al[24], who pioneered the mineralization method for BP preparation by using red phosphorus (RP) as the phosphorus source in combination with an Au-Sn-SnI₄ catalyst. This method features relatively mild reaction conditions (ambient or low pressure), simple operation, cost-effectiveness, and tunable crystallinity and high yield of BP, attracting wide attention for scalable BP preparation. To decrease the catalyst cost, Zhao et al.[25] developed a precious metal-free P-Sn-I catalyst for preparing BP. However, the composition of P-Sn-I and the underlying catalytic mechanism for the formation of BP remain unclear. Li et al.[26]Further revealed that the ternary Sn₂₄P_19.3I₈ is a key catalyst for the preparation of BP, which formed via a vapor-solid-solid (VSS) growth mechanism. Despite this, synthesis of Sn₂₄P_19.3I₈ catalyst involves multiple sealing, grinding and high-temperature annealing steps, resulting in too long synthesis period (10-day) and low efficiency of BP production.

To promote 10 days thesis of Sn₂₄P_19.3I_8, a multi-stage heating and cooling means was proposed in our previously work[27], which sharply reduced the catalyst preparation period from 10 days to 30 hours for the experiment. Regretfully, the obtained Sn₂₄P_19.3I₈ catalyst underwent progressive sintering at elevated temperature, leading to shortened cycle life for BP preparation. At present, the deactivation mechanism of Sn₂₄P_19.3I₈ catalyst is still unclear. Moreover, the insufficient catalytic performance of Sn₂₄P_19.3I₈ restricts the efficient and large-scale preparation of BP.

In this work, the origin of rapid thermal sintering and catalytic deactivation of Sn₂₄P_19.3I₈ during BP preparation was confirmed to local heat accumulation due to the intrinsically low thermal conductivity of Sn₂₄P_19.3I₈. Inspired by this inference, graphite with superior thermal conductivity was incorporated with Sn₂₄P_19.3I₈ to construct a Sn₂₄P_19.3I₈/Gra composite catalyst. Expectedly, for BP preparation, the introduction of graphite effectively improved the thermal conductivity of Sn₂₄P_19.3I₈ and inhibits local heat accumulation, significantly enhancing thermal stability and catalytic activity of Sn₂₄P_19.3I₈/Gra. This work provides a feasible strategy for efficient BP preparation by designing a highly stable Sn₂₄P_19.3I₈/Gra catalyst, laying the foundation for the efficient industrial production and application of BP.

2. Experimental

2.1. Synthesis of Sn₂₄P_19.3I₈ and Sn₂₄P_19.3I₈/Gra catalysts

For the general synthesis of Sn₂₄P_19.3I_8, red phosphorus (RP, 2.04 g, Damao), tin (IV) iodide (SnI₄, 3.75 g, BP technology), and tin powder (Sn, 7.83g, Guangsheng) with desired stoichiometric were thoroughly homogenized via mortar grinding. Then, the resulted mixture was subsequently sealed within a vacuum-quenched quartz tube and heated to 550°C at a ramp rate of 5°C/min in a muffle furnace. After holding at this temperature for 30 min, the temperature was reduced to 500 ℃ within 225 minutes and held for 30 min. Subsequently, the temperature rose again to 550°C within 10 minutes. The above thermal treatment was repeated six times for the formation of Sn₂₄P_19.3I₈ ingot which was further mechanically pulverized and sifted through a 200-mesh sieve to obtain fine Sn₂₄P_19.3I₈ powder.

Synthesis of granular Sn₂₄P_19.3I₈ catalyst. 4.0 g of fine Sn₂₄P_19.3I₈ powder was compressed to a dense monolith under a uniaxial pressure of 20 MPa for 30 minutes. The dense monolith was then crushed and sieved, yielding isolated particles with a controlled size distribution of 5–8 mesh.

Synthesis of granular Sn₂₄P_19.3I₈/Gra catalyst. Fine Sn₂₄P_19.3I₈ powder and graphite with a mass ratio of 5:2 was ball milled (500 rpm, 24 h) to obtain uniform mixture, which was then compressed, crushed, and sieved to obtain granular Sn₂₄P_19.3I₈/Gra catalyst.

2.2. Preparation of BP

2 g of RP and 1 g of Sn₂₄P_19.3I₈ or 1.4 g of Sn₂₄P_19.3I₈/graphite catalyst (both catalysts have equivalent active catalyst mass) were placed at the high and intermediate temperature zones of a quartz tube, respectively. BP was formed in a low temperature zone. The three zones were separated by nickel foam spacers. After vacuuming, the quartz tube is sealed and placed in a dual-zone tube furnace, where the high and low temperature zones were heated to 520°C and 500°C within 200 min. After reaction for 12 h, the furnace was cooled to room temperature. The obtained BP crystals were collected and stored in a glovebox for further characterization.

2.3. Characterizations

The crystal structure and phase composition of the synthesized materials were analyzed using X-ray diffraction (XRD) with Cu Kα radiation (λ = 1.5418 Å). Raman spectroscopy was performed to determine the composition and structure of the substance, employing a 532 nm laser source and a spectral range of 50-4000 cm^− 1. Scanning electron microscope (SEM) was utilized to observe the microscopic morphology of catalyst and BP surface. Elemental composition and spatial distribution analysis were conducted using an energy-dispersive X-ray spectroscopy (EDS) system attached to the SEM. The thermal conductivity of the catalyst samples was quantified via a thermal conductivity analyzer, while the specific surface area of catalyst was determined using the Brunauer-Emmett-Teller (BET) method.

3. Results and discussion

3.1 Inactivation analysis of pure Sn₂₄P_19.3I₈ catalyst

To further reveal the origin of sintering, in situ thermal monitoring via precision thermocouples was used to examine the localized temperature variations within the Sn₂₄P_19.3I₈ catalyst during BP preparation. As depicted in Fig. 1a, the quartz tube showed a distinct change in color after the first BP preparation. The color of the middle zone of the quartz tube containing the catalyst has changed from black to brown, suggesting RP has been catalyzed and transformed into some kind of substance by Sn₂₄P_19.3I₈ catalyst. The black product was collected in the low-temperature zone of the quartz tube and was confirmed to be BP. For the first cycle of BP preparation by using fresh (before use) Sn₂₄P_19.3I₈ catalyst, a high yield of 87% was achieved. However, Sn₂₄P_19.3I₈ catalyst has suffered severe sintering (Fig. 1c). When this sintered Sn₂₄P_19.3I₈ catalyst (after use in the first preparation of BP) was subsequently employed for a second cycle of BP preparation, most of the RP was not catalytically converted into BP, with substantial deposition of RP along the reactor walls, leading to a significant drop in BP yield of 56% (Fig. 1b). XRD analysis revealed no detectable changes in the crystal structure of the fresh (before BP preparation) and used (after BP preparation) Sn₂₄P_19.3I₈ catalysts, as evidenced by the consistent diffraction peaks in Fig. 1d, suggesting crystal phase stability without the formation of new compounds or impurity phases. BET measurements (Table. 1) demonstrate that Sn₂₄P_19.3I₈ exhibited a pronounced decline in specific surface area from 1.4105 m²/g to 0.3660 m²/g and mesopore volume from 0.0055 cm³/g to 0.0010 cm³/g after use for BP preparation, which is consistent with the particle aggregation observed in Fig. 1c. These results indicate that sintering after the first application in BP preparation is the primary reason for the performance degradation of Sn₂₄P_19.3I₈ catalyst.

Moreover, local temperature within the catalyst was measured by in situ thermal monitoring via precision thermocouple (left in Fig. 1e) during high-temperature BP preparation. The initial temperature of the catalyst was measured to be 500°C. As the reaction proceeds, the measured temperature was raised to 510°C and 530°C at 1 h and 6 h during BP preparation (middle and right in Fig. 1e), indicating exothermic features of the catalytic reaction. The thermal conductivity of fresh Sn₂₄P_19.3I₈ was quantified at room temperature, yielding a low value of 1.73 W·m⁻¹·K⁻¹. Such poor thermal conductivity impedes heat dissipation and promotes localized thermal accumulation, which resulted in particle sintering and sharp reduced specific surface area, ultimately degrading catalytic performance. Based on this inference, compounding with carbon, which has excellent thermal conductivity, is a promising method to improve the catalytic stability of Sn₂₄P_19.3I₈ for BP preparation.

3. 2 Synthesis of Sn₂₄P_19.3I₈/Gra composite catalyst

In order to enhance the high-temperature stability of the Sn₂₄P_19.3I₈ for BP preparation, graphite was compounded with Sn₂₄P_19.3I₈ due to the intrinsically high thermal conductivity, large specific surface area, and exceptional mechanical strength[28–30]. The Sn₂₄P_19.3I₈/graphite (abbreviated as Sn₂₄P_19.3I₈/Gra) composite catalyst was synthesized by ball milling, tablet pressing, crushing and sieving, as schematically shown in Fig. 2a. A comprehensive investigation indicates that the optimal Sn₂₄P_19.3I₈: graphite mass ratio of 5:2 and palletization conditions of 20 MPa for 30 minutes yield a structurally complete disco of composite catalyst, without detectable powder shedding or structural fracture. It should be noted that further increasing the graphite ratio is not considerable due to no catalytic activity for the formation of BP.

The XRD pattern of the optimal Sn₂₄P_19.3I₈/Gra composite catalyst (Fig. 3a) exhibits characteristic diffraction peaks of crystalline Sn₂₄P_19.3I₈ and (002) peak of graphite at 26.5° (PDF#75-1621) without any impurity. The SEM images and the corresponding EDS mappings of pure Sn₂₄P_19.3I₈ (Fig. 3b, c) and Sn₂₄P_19.3I₈/Gra (Fig. 3d, e, f) show that, the combination of graphite with Sn₂₄P_19.3I₈ induces a remarkable improvement in the spatial distribution homogeneity of Sn, P, and I elements. This improved homogeneity of Sn₂₄P_19.3I₈ across the carbon matrix not only facilitates accessibility of active sites, but also enhances the heat transfer to alleviate sintering, therefore enhancing structure stability for high temperature catalysis of BP preparation.

3.3 Catalytic evaluation of Sn₂₄P_19.3I₈/Gra catalyst

The catalytic performance of fresh Sn₂₄P_19.3I₈/Gra composite catalyst for BP preparation was systematically evaluated and compared to that of fresh pure Sn₂₄P_19.3I₈ catalyst. 2 g of RP was used as the phosphorus source for BP preparation. To reveal the effect of catalyst content on the BP yield, 1.4 g, 0.7 g and 0.42 g of Sn₂₄P_19.3I₈/Gra or 1.0 g, 0.5 g and 0.3 g of Sn₂₄P_19.3I₈ were used for three BP preparation experiments. The active Sn₂₄P_19.3I₈ content in Sn₂₄P_19.3I₈/Gra composite catalyst was consistent with that of pure Sn₂₄P_19.3I₈ catalyst. Figure 4a displays the quartz tubes with different masses of Sn₂₄P_19.3I₈ and Sn₂₄P_19.3I₈/Gra catalysts after BP preparation. There were some unreacted RP on the quartz tube wall for the BP preparation employing 0.5 g and 0.3 g of pure Sn₂₄P_19.3I₈ catalyst, indicating relatively low BP yield. As illustrated in Fig. 4b, the first BP yields using Sn₂₄P_19.3I₈/Gra composite were much higher than those using pure Sn₂₄P_19.3I₈ with different catalyst contents. Notably, the Sn₂₄P_19.3I₈/Gra composite catalyst exhibited no observable sintering after high temperature catalysis for BP preparation, whereas pure Sn₂₄P_19.3I₈ underwent significant particle agglomeration in the same conditions, underscoring the key role of graphite in improving catalytic performance.

Furthermore, the cycling stability of the Sn₂₄P_19.3I₈/Gra composite catalyst was investigated through continuous BP preparation. As shown in Fig. 4c, only trace amounts of unreacted RP can be observed, demonstrating remarkable catalytic stability. Moreover, even though the BP yield decreases as the BP preparation cycle increases, the BP yield remains a high value of 83.3% (Fig. 4d). The Sn₂₄P_19.3I₈/Gra composite catalyst displayed a little change in BET specific surface area from 1.8984 m²/g to 1.8840 m²/g after continuous nine cycles of BP preparation. Despite this, the pore volume of Sn₂₄P_19.3I₈/Gra composite catalyst was largely decreased from 0.007280 cm³/g to 0.0035 cm³/g, mainly the result of black phosphorus covering the pore structure. This distinctly decreased pore volume was attributed to the decrease in BP yield.

The superior catalytic performance of Sn₂₄P_19.3I₈/Gra composite catalyst was attributable to the enhanced thermal conductivity (15.75 W·m⁻¹·K⁻¹), which was nine-folds higher than that of pure Sn₂₄P_19.3I₈ (1.73 W·m⁻¹·K⁻¹). Therefore, the temperature of Sn₂₄P_19.3I₈/Gra composite catalyst showed small change during BP preparation (Fig. 5a), with a measured temperature of 510°C and 515°C at 1 h and 6 h during BP preparation. These comprehensive results demonstrate that, by accelerating the heat transfer in catalyst, the integration of graphite overcomes the sintering of pure Sn₂₄P_19.3I₈ catalyst and therefore improves the catalytic performance of Sn₂₄P_19.3I₈/Gra composite catalyst for BP preparation.

The structure of the obtained BP using Sn₂₄P_19.3I₈/Gra composite catalyst was characterized by XRD, Raman, EDS, and SEM. As shown in Fig. 5b, the XRD pattern exhibits distinct diffraction peaks at 16.99°, 26.55°, 34.24°, and 52.26°, corresponding to the (020), (021), (040), and (060) planes of orthorhombic BP (PDF#73-1358), respectively. The absence of impurity peaks confirms the high phase purity of the prepared BP. Raman analysis (Fig. 5c) further validates the crystalline quality of BP, with characteristic vibrational modes observed at 357.6 cm⁻¹ (A_g¹), 433.7 cm⁻¹ (B_2g), and 461.8 cm⁻¹ (A_g²). The well-defined peaks and lack of extraneous signals corroborate the excellent crystallinity and structural integrity of the product. The EDS analysis (Fig. 5d) reveals the main existence of phosphorus, with trace amounts of adsorbed oxygen in the prepared BP. The SEM image (inset in Fig. 5d) reveals the characteristic layered structure of BP, which is consistent with previous reports. Collectively, these results unambiguously demonstrate that the stable Sn₂₄P_19.3I₈/Gra composite catalyst enables the efficient synthesis of highly crystalline and phase-pure BP with high yield.

4. Conclusion

In summary, we revealed that the deactivation of pure Sn₂₄P_19.3I₈ catalyst during BP preparation was primarily due to its poor thermal conductivity, which led to uneven heat distribution and severe sintering, largely decreased the catalytic performance. To address this issue, Sn₂₄P_19.3I₈ was integrated with graphite to construct a Sn₂₄P_19.3I₈/Gra composite catalyst with thermal conductivity for BP preparation. This composite catalyst exhibited superior catalytic activity and stability, with a high yield of 83.3% at the ninth cycle of BP preparation. This work provided a feasible strategy for designing a high-performance BP preparation catalyst, promoting the large-scale production and application of BP.

Ethics and Consent to Participate:

Not applicable. This study did not involve any human participants, animal experiments, or the use of clinical data.

Table 1

BET test results of Sn₂₄P_19.3I₈ before and after use for BP preparation.
Catalyst	Surface area (m²/g)	Pore volume (m³/g)
Before BP preparation	1.4105	0.0055
After BP preparation	0.3660	0.0010

Table 2

The morphology features of the Sn₂₄P_19.3I₈/Gra composite catalyst synthesized under different conditions.
NO.	Sn₂₄P_19.3I₈:graphite mass ratio	Time (min)	Pressure (MPa)	State
1	——	30	15	not formed
2	——	30	20	fractures
3	5:1	30	15	looseness
4	5:1	30	20	looseness
5	5:2	30	15	abscission
6	5:2	30	20	tight (optimal catalyst)
7	5:3	30	15	tight
8	5:3	30	20	tight

Table 3

BET test results of Sn₂₄P_19.3I₈/Gra before and after BP preparation.
Catalyst	Surface area (m²/g)	Pore volume (cm³/g)
Before BP preparation	1.8984	0.0072
After nine cycles of BP preparation	1.8840	0.0035

Consent for Publication

Not applicable. This manuscript does not contain any individual person’s data in any form.

Competing Interest:

The authors declare no conflict of interest.

Author Contribution

Tun Nile: Investigation, Data analysis, Writing -original draft. Hao Sun: Resources, Data curation. Tingting Xu: Conceptualization, Methodology. Yu Yang: Formal analysis. Caimei He: Conceptualization. Wen Chen: Investigation. Peichao Lian: Conceptualization, Funding acquisition.

Funding

This work was supported by National Natural Science Foundation of China (22168021).

Data Availability

Data will be made available on request.

Acknowledgments

Not applicable.

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Yes