高压固相拓扑聚合合成纳米碳材料

费云帆; 李阔; 郑海燕

doi:10.11858/gywlxb.20230749

高压固相拓扑聚合合成纳米碳材料

doi: 10.11858/gywlxb.20230749

北京高压科学研究中心, 北京　100193

基金项目: 国家自然科学基金（22022101，21875006，21771011）；国家重点研发计划（2019YFA0708502）

详细信息

作者简介:
费云帆（2000－），男，博士研究生，主要从事高压下碳材料的精准合成研究. E-mail：yunfan.fei@hpstar.ac.cn

通讯作者:
郑海燕（1982－），女，博士，研究员，主要从事碳基材料高压精准合成研究. E-mail：zhenghy@hpstar.ac.cn

中图分类号: O521.2
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出版历程
- 收稿日期: 2023-10-13
- 修回日期: 2023-11-13
- 录用日期: 2023-11-13
- 刊出日期: 2023-12-15

Synthesis of Nano-Carbon Materials by High Pressure Solid-State Topochemical Polymerization

Center for High Pressure Science and Technology Advanced Research, Beijing 100193, China

摘要

摘要: 碳原子多样的杂化方式使得碳材料具有复杂的结构和性能。寻找并开发具有新结构的碳材料，实现碳材料的精准可控合成是碳材料研究的重要方向。高压（高于1 GPa）可以有效地压缩分子间距，促进不饱和分子发生聚合，为“自下而上”合成碳材料提供了新的策略与机遇。高压下的化学反应多为固相反应，反应分子受到晶格的约束，表现出拓扑化学反应的特点。这意味着可以通过控制反应物的晶体结构调控反应路线，进而合成具有特定结构和功能的碳材料。本文报道了利用高压固相拓扑聚合方法合成聚烯烃、聚炔化合物、金刚石基纳米线、碳纳米带、石墨烷以及高电荷离子型聚合物等多种碳材料的研究进展，并简要介绍高压下化学反应的特点与机制。
- 高压化学 /
- 纳米碳材料 /
- 压力诱导聚合 /
- 固相拓扑聚合 /
- 氢转移
Abstract: The various hybridization states of carbon atoms endow carbon materials with complex structures and properties. Finding and developing carbon materials with new structures and realizing accurate and controllable synthesis of carbon materials are important directions in the carbon materials research area. High pressure (above 1 GPa) can effectively reduce the intermolecular distances and promote the polymerizations of unsaturated molecules, which provides a new strategy and opportunity for “bottom-up” synthesis of carbon materials. The chemical reaction under high pressure is generally the solid phase reaction and the reaction molecules are constrained by the lattice, which shows the characteristics of topochemical reaction. This means that we can adjust the reaction routes by controlling the crystal structures of reactants to synthesize carbon materials with specific structures and functions. In this review, we report the progress in the synthesis of carbon materials by high pressure solid-state topochemical polymerization, such as polyolefin, acetylenic polymer, diamond-based carbon nanothreads, carbon nanoribbons, graphane and high-charge ionic polymers, and briefly introduce the characteristics and mechanism of chemical reaction under high pressure.
- high pressure chemistry /
- nano-carbon materials /
- pressure induced polymerization /
- solid-state topochemical polymerization /
- hydrogen transfer

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Nanoscale inorganic materials with unique electrical, optical and mechanical properties, which are distinct from their bulk counterparts, attract attention in both fundamental scientific research and industrial applications^[1-3]. Investigations on the phase transformation and the structural stability of nanomaterials under high pressure are conducted in physics, materials science, geophysics^[4-9]. Numerous studies on nanomaterials under high pressure have revealed that the grain size plays an important role in the pressure-induced phase transition behaviors. A number of interesting high-pressure behaviors and new properties in nanomaterials appear when the grain size is smaller than a critical size. Studies on CdSe, CdS, ZnO and ZnS nanocrystals observe the size-dependent phase transformations^[10-13]. Lv, et al.^[14] reports that the Mn₃O₄ nanoparticles show a different phase transformation route and a new high-pressure phase at 14.5–23.5 GPa, which has been recognized to be the orthorhombic CaTi₂O₄-type structure. The crystalline-amorphous transition is discovered in materials such as Y₂O₃, TiO₂, PbTe and BaF₂^[15-19]. Therefore, high-pressure studies on nanomaterials are significant for the discovery of new structures and properties of materials.

Calcium fluoride (CaF₂), a typical face-centered-cubic ionic crystal, has been widely used in many fields^[2-3]. Due to its simple crystal structure, CaF₂ becomes an ideal material for high-pressure research. High-pressure X-ray diffraction (XRD) and Raman spectroscopy studies of bulk CaF₂ have shown that it undergoes two structural transitions and finally reaches highly coordinated structures. The pressure-induced phase transition from the fluorite structure (space group: Fm3m) to the α-PbCl₂-type structure (space group: Pnma) has been found in the pressure range of 8–10 GPa^[20-21]. Dorfman, et al.^[22] have reported that bulk CaF₂ transforms from the α-PbCl₂-type structure into the hexagonal structure at 79 GPa and 2 000 K. Inspired by the size effect of nano-sized materials, our group has made progresses in different structural phase transitions and in the compressibility for nanosized MF₂ (M=Ca, Sr, Ba) particles at high pressures^{[19, 23-26]}. Previous high-pressure studies on the 8 nm CaF₂ nanocrystals reveals that the structural phase transition from the fluorite-type structure into the orthorhombic α-PbCl₂-type structure starts at 14 GPa, and the transition pressure is higher than that of the bulk CaF₂^[23]. Recently, we have performed high-pressure studies on the 23 nm CaF₂ nanocrystals up to 23.5 GPa using synchrotron XRD measurement. We have found that the transition from the fluorite to the orthorhombic phase occurrs at 9.5 GPa, significantly lower than the transition pressure of the 8 nm CaF₂ nanocrystals, but close to that of the bulk materials^[24]. Further analysis indicates that the defect effect in the 23 nm CaF₂ nanocrystals plays a key role in the structural stability. Nevertheless, the high pressure induced structural phase transition of the CaF₂ nanocrystals with other sizes has not been reported. The phase-transition mechanism and the compressibility of the nanoscale CaF₂ are still unclear. In order to further investigate the high pressure behaviors of the nanosized CaF₂, and to confirm whether there is a size-dependent phase transformation at high pressure, more high pressure experimental data for various sized CaF₂ nanocrystals is urgently needed.

Here we investigate the high-pressure behaviors of the CaF₂ nanocrystals with an average grain size of 11 nm using in-situ XRD. We analyse the phase stability, the bulk modulus and the compressibility of the synthesized 11 nm-sized CaF₂ nanocrystals in details. Through comparing the high pressure experimental data of different sized CaF₂ materials, the main factor influencing the structural stability and compression properties of the CaF₂ nanomaterials is explored.

1. Materials and Methods

The 11 nm-sized CaF₂ nanocrystals were prepared by a typical synthesis procedure, as reported in literatures^[27-28]. 2 mmol Ca(NO₃)₂ and 4 mmol NaF were added into a mixture which consisted of ethanol, oil acid, and sodium hydroxide. After being vigorously stirred, the white suspension was transferred into a 40 mL autoclave. The heat-treatment condition at a temperature of 160℃ was maintained for 24 h. Then, the autoclave was cooled down to room temperature, and the final products were collected after centrifugation and drying treatments.

The crystalline structure, the morphology and the particle size of the CaF₂ nanocrystals were examined by XRD (D8 DISCOVER GADDS) with Cu K_α radiation ( $\lambda$ =1.5418 Å) and by high-resolution transmission electron microscopy (HRTEM, H-7500). The sample was loaded into a diamond anvil cell (DAC) with a culet size of 400 μm for high-pressure analysis. The fluorescence shift of the ruby R1 line was utilized to calibrate the pressure, and an methanol-ethanol mixture with a volume ratio of 4∶1 was chosen as the pressure-transmitting medium. High-pressure XRD experiment was performed at B2 High-Pressure Station of Cornell High Energy Synchrotron Source (CHESS) with a wavelength of 0.485946 Å. MAR165 CCD detector was used to collect the XRD data. The 2D XRD images were integrated using FIT2D software. Materials Studio program was performed to refine the crystal structure using the high-pressure synchrotron XRD patterns.

2. Results and Discussion

Fig.1(a) exhibits the dimension and the morphology of the synthesized CaF₂ nanocrystals, and the corresponding particles’ size distribution histogram is presented in Fig.1(b). Fig.1 reveals that all the nanoparticles are well dispersed and almost sphere with an average diameter of (11 ± 2) nm. The selected-area electron diffraction (SAED) pattern (inset in Fig.1(a)) shows that the major diffraction rings of the fluorite structure, indicating that the synthezied CaF₂ nanocrystals have probably the fluorite structure.

Figure 1. (a) TEM image of the as-synthesized CaF₂ nanocrystals; (b) particle size distribution of the CaF₂ nanocrystals

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Fig.2 presents the Rietveld refinement of the diffraction pattern of the synthesized CaF₂ nano-particles at ambient conditions. The great agreement between simulations and XRD experiments at ambient conditions with the residuals R_wp=7.73% and R_p=5.99% unraveled that the ambient pressure phase adopts a fluorite structure with a space group of Fm3m. The fluorite structure is constructed by the Ca atoms occupying the (0, 0, 0) positions and by the F atoms occupying the (0.25, 0.25, 0.25) positions. The cubic structure has an lattice constant of 5.461(2) Å. It is consistent with the value of a₀=5.463 Å (JCPDS Card No. 35-0816).

Figure 2. Rietveld refinement of the diffraction pattern of the synthesized CaF₂ nanoparticles (Red dots, upper (blue), and lower (black) solid lines represent experimental, calculated, and residual patterns, respectively.)

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Fig.3 displays the selected high-pressure XRD patterns of the CaF₂ nanocrystals under different pressures up to 28.6 GPa. At 1.0 GPa, six diffraction peaks of (111)_c, (220)_c, (311)_c, (400)_c, (331)_c and (422)_c of the CaF₂ nanocrystals are observed, together with one peak of the T-301 stainless steel gasket (marked by asterisk). When the pressure reaches 12 GPa, the (111) diffraction peak becomes asymmetric, and a new diffraction peak starts to appear at the right side of the (111) peak, which indicates the occurrence of a phase transition from the fluorite structure to the α-PbCl₂-type structure. The transition pressure is much higher than the one reported in the bulk CaF₂ materials and slightly lower than that of the 8 nm-sized CaF₂ nanocrystals^[23]. When the pressure increases to 20.8 GPa, all the diffraction peaks (120)_o, (111)_o, (121)_o, (211)_o, (031)_o, (002)_o and (240)_o can be assigned to the arised high pressure phase, illustrating the completion of the phase transition. The α-PbCl₂-type structure is stable up to 28.6 GPa (the highest pressure in this study). Then the sample is decompressed to ambient pressure, and it turns out that the pure high-pressure α-PbCl₂-type structure is retained, which indicates the phase transformation is irreversible. Fig.4 presents the Rietveld refinement of the diffraction pattern of the CaF₂ nanocrystals at ambient conditions after decompression, and it shows a quite good agreement with the α-PbCl₂-type structure (with the residual R_wp=0.40 %).

Figure 3. High-pressure XRD patterns of the CaF₂ nanocrystals, in which the peak (marked by asterisk) is derived from the gasket

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Figure 4. Rietveld refinement of the diffraction pattern of the CaF₂ nanocrystals at ambient conditions after decompression (Red dots, upper (blue), and lower (black) lines represent experimental, calculated, and residual patterns, respectively.)

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Fig.5 shows the compressibility of the CaF₂ nanocrystals. A third-order Birch-Murnaghan (BM) equation of state (EOS) is fitted to the experimental p-V data^[29]

Figure 5. Unit-cell volume as a function of pressure determined for the 11 nm-sized CaF₂ nanocrystals (Solid curves are the Birch-Murnaghan EOS fits to the experimental data. Error bars are observed when they are large enough to exceed the sizes of the marked dots.)

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$p = (3/2)B_0[(V/V_0)^{-7/3} - (V/V_0)^{-5/3}] \left\{1 + (3/4)(B_0' - 4)×[(V/V_0)^{-2/3} - 1]\right\}$

(1)

where V₀ is the zero-pressure volume, V is the volume at pressure p given in GPa (V₀ and V were calculated by JADE program), B₀ is the isothermal bulk modulus, ${{B}}_0'$ is the first pressure derivative of the bulk modulus. For the CaF₂ nanocrystals, the fitting yield B₀ = 109(5) GPa, ${{B}}_0'$ = 5 for the fluorite structure, and B₀ = 89(1) GPa, ${{B}}_0'$ = 4 for the α-PbCl₂-type structure. The isothermal bulk modulus of the α-PbCl₂-type phase is lower than that of the fluorite phase. The lower bulk modulus of the high-pressure phase of the CaF₂ nanocrystals at high pressure indicates a higher compressibility. This result is consistent with the previous studies on the bulk CaF₂, but it is different from the bulks SrF₂ and BaF₂ which have lower compressibility under high pressure^{[22, 30]}. The bulk moduli of the 11 nm-sized CaF₂ nanocrystals for the fluorite and the α-PbCl₂-type structure are both significantly larger than those of the bulk CaF₂^[21–22] and the 23 nm-sized CaF₂ nanocrystals^[24], indicating a higher incompressibility for the CaF₂ nanocrystals with smaller grain size. In terms of the Hall-Petch effect^[31-32], a continuous decrease of grain size could further elevate material hardness, thus, the increase in bulk modulus of 11 nm-sized CaF₂ nanocrystals can be easily understood.

Table 1 summarizes the phase transition pressure (p_T), the EOS parameters (B₀ and $B_{0}'$ ) of the bulk CaF₂ and the CaF₂ nanocrystals with different grain sizes, which clearly reveals the differences between the bulk and the nanoscale CaF₂. It is found that the phase transition pressure and the bulk modulus of the 11 nm-sized CaF₂ nanocrystals are higher than those of the bulk CaF₂ and the 23 nm-sized CaF₂ nanocrystals. A large number of high pressure investigations indicate that many nanomaterials (e.g., CdSe, ZnS and PbS) exhibit obvious elevations of structural stability compared with their bulk materials, which is attributed to the higher surface energies in nanomaterials^{[10, 13, 33]}. Compared with the bulk CaF₂ and the 23 nm-sized CaF₂ nanocrystals, a relatively higher surface energy is expected for the 11 nm-sized CaF₂ nanocrystals, and thus the elevations both in the transition pressure and in the bulk modulus can be easily understood.

Table 1. Transition pressure (

${p}{_{\rm T}}$ ), and EOS parameters (B₀ and B₀ ′) of the fluorite-type and the α-PbCl₂-type CaF₂

Morphology	Size	$p{_{\rm T}}$ /GPa	${B{_0 } }$ /GPa		B₀ ′
Morphology	Size	$p{_{\rm T}}$ /GPa	Fm3m	Pnma	Fm3m	Pnma
Bulk	Micro	9.5^[21]	87(5)^[21]	74(5)^[22]	5	4.7
		9^[34]	81(1)^[34]		5.22
		8.1^[20]	79.54^[20]	70.92^[20]	4.54	4.38
Nanocrystals	8 nm	14^[23]	112(6)	93(9)	5	4
	23 nm	9.5^[24]	103(2)^[24]	78(2)^[24]	5	4
	11 nm	12	109(5)	89(1)	5	4

| Show Table

DownLoad: CSV

Besides the different high-pressure behaviors with the bulk CaF₂ and the 23 nm-sized CaF₂ nanocrystals, Table 1 shows that the 11 nm-sized CaF₂ nanocrystals exhibit a lower transition pressure^[23] and a lower bulk modulus compared with the 8 nm-sized CaF₂ nanocrystals. To the best of our knowledge, defects and grain size are considered to be the main factors in influencing the high-pressure behaviors of the 11 nm-sized CaF₂ nanocrystals and the 8 nm-sized CaF₂ nanocrystals. For further analyses, we have carried out HRTEM measurements of many grains of the 11 nm-sized CaF₂. The HRTEM image is given in Fig.6, it shows that the 11 nm-sized CaF₂ nanocrystals have no visible defects and dislocations, indicating a relatively low defect concentration. Obviously, the decrease of the transition pressure in the 11 nm-sized CaF₂ nanocrystals cannot be attributed to the defects (or dislocation) effect. Therefore, the differences in the phase transformations between the 11 nm and the 8 nm-sized CaF₂ nanocrystals may be caused by the grain size effect. The 8 nm-sized CaF₂ nanocrystals, which have a smaller grain size, possess a higher surface energy, that could result in the elevation of the phase transition pressure.

Figure 6. HRTEM image of the as-synthesized 11 nm-sized CaF₂ nanocrystals.

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Our results illustrate that the transition pressure dramatically increases as the size of the grains decreases, and the CaF₂ nanocrystals show a noticeable size-dependence of phase transformation at high pressure when the grain size below 11 nm. Therefore, it can be reasonably concluded that the critical size of the CaF₂ nanocrystals, marking the oneset of nanoscal effect, is larger than 11 nm. For the 11 nm-sized CaF₂ nanocrystals, the high-pressure metastable structure (α-PbCl₂-type structure) is retained after the pressure is released, without observing the fluorite structure. This result is in good accordance with the oberservation for the 8 nm-sized CaF₂ nanocrystals^[23], but it is different with those of the bulk CaF₂ and the 23 nm-sized CaF₂ nanocrystals whose transformations are completely or partially reversible^{[21, 24]}. The inreversibility of the 11 nm-sized CaF₂ nanocrystals might be due to the high surface energy, which lead to the solid-solid phase transition hysteresis after decompression. Discovering novel high-pressure metastable structure is one of the main purposes of the high pressure study of the CaF₂ nanocrystals.

3. Conclusions

In summary, the high-pressure behaviors of the CaF₂ nanocrystals with an average grain size of 11 nm have been investigated by in-situ XRD. The phase transition from the fluorite structure to the α-PbCl₂-type structure occurrs at 12 GPa, which is much higher than the value observed for the bulk CaF₂ and slightly lower than that of the 8 nm-sized CaF₂ nanocrystals. The bulk moduli of the CaF₂ nanocrystals with the fluorite or the α-PbCl₂-type structures are all larger than those of the bulk CaF₂, indicating a high incompressibility of nanosized CaF₂. The pure α-PbCl₂-type metastable structure is retained in the 11 nm-sized CaF₂ nanocrystals after decompression. Such distinct high-pressure behaviors of the 11 nm-sized CaF₂ nanocrystals are considered to be mainly due to the grain size effect. When the size is below the critical size, the high surface energy begins directing the enhancement of the structural stability and the increase of the bulk modulus.

图 1 在0.2 GPa、99 K时乙烯Ⅰ相（P2₁/n, $C_{2h}^5$ , Z = 2）的晶体结构^[40]（升压产生的各向异性压缩（沿b轴减小16.7%，沿a和c轴分别减小约2%）使沿a轴的最近邻分子的碳原子间距(3.527 Å)与位于晶胞顶点和中心的分子之间的碳原子间距（3.635 Å）相当）

Figure 1. Crystal structure of ethylene in phase Ⅰ (P2₁/n, $C_{2h}^5$ ,Z = 2) at 0.2 GPa and 99 K^[40] (This anisotropic compressibility generated by increasing pressure (the cell decreases by 16.7% along the b axis and about 2% along the a and c axis respectively) makes the distances between C atoms of the nearest neighbor molecules located along the a axis (3.527 Å) comparable to those between the molecules sitting on thevertex and at the center of the cell (3.635 Å).)

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图 2 (a) 氘代丁炔二酸（deuterated ADCA，ADCA-d₂）在8 GPa时的晶体结构^[61]（绿色和紫色箭头分别代表C···C间距和O···D间距）；(b) 300 K、9 GPa时ADCA的分子动力学模拟结果^[61]；(c) 从16 GPa回收的产物的晶体结构^[61]

Figure 2. (a) Crystal structure of ADCA-d₂ at 8 GPa^[61] ( The green and purple arrows indicate the C···C and O···D distances respectively); (b) molecular dynamics simulation of ADCA at 300 K and 9 GPa^[61]; (c) crystal structure of the product recovered from 16 GPa^[61]

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图 3 一维sp³ C-H纳米线的3种预测结构^[72]

Figure 3. Three predicted structures of one-dimensional sp³ C-H nanothreads^[72]

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图 4 沿c轴(a)和垂直于c轴(b)的tube (3,0)氮化碳纳米线的结构^[80]

Figure 4. Structure of tube (3,0) carbon nitride nanothreads viewed along the c-axis (a) and perpendicular to the c-axis (b)^[80]

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图 5 (a)噻吩的光学显微照片^[83]；(b)噻吩通过[4+2]Diels-Alder反应生成反式-噻吩衍生纳米线的反应机制^[83]

Figure 5. (a) Optical micrograph of thiofuran^[83]; (b) mechanism of formation of anti-thiophene-derived nanothreads by [4+2] Diels-Alder reaction^[83]

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图 6 (a) 哒嗪在0.61 GPa时的局部π堆积结构^[88]（d_c为哒嗪环的质心距离；d_p为平行平面之间的距离；Φ为哒嗪环之间的滑移角，由环的法向量和质心向量确定）；(b) 哒嗪沿a轴的堆积^[88]；(c) 哒嗪在0 GPa、500 K下的反应示意图^[88]

Figure 6. (a) π-stacking structure of pyridazine at 0.61 GPa^[88]， in which d_c is the centroid distance between pyridazine rings, d_p is the distance between parallel planes, and Φ is the slippage angle between pyridazine rings, defined by the ring normal and centroid vectors; (b) the stacking of pyridazine along a-axis^[88]; (c) diagram of the reaction of pyridazine at 30 GPa and 500 K^[88]

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图 7 (a) s-三嗪在室温高压下的原位X射线衍射^[89]（D表示降压过程）；(b) 在573 K、10.2 GPa下回收产物的X射线衍射图像^[89]；(c) s-三嗪在12.1 GPa下的晶体结构^[89]；(d)反应路径中各阶段的焓变（红线和黑线分别表示分步和协同反应过程）^[89]；(e) s-三嗪的前线分子轨道^[89]

Figure 7. (a) In situ XRD of s-triazine at high pressure and room temperature^[89], in which D represents the decompression process;(b) XRD of the product recovered from 573 K and 10.2 GPa^[89]; (c) the crystal structure of s-triazine at 12.1 GPa^[89];(d) enthalpy versus step curves of each stage in the reaction path (Red and black lines represent the stepwise and concerted process, respectively)^[89]; (e) molecular orbitals of s-triazine^[89]

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图 8 (a) 0.84 GPa时苯胺相Ⅱ的晶体结构沿b轴的投影^[91]；(b) 密度泛函理论计算优化的一维苯胺衍生纳米线结构^[92]

Figure 8. (a) Crystal structure of aniline phase Ⅱ at 0.84 GPa projected along the b-axis^[91]; (b) structure of one-dimensional aniline-derived nanothreads optimized by DFT^[92]

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图 9 (a) 10.8 GPa时FDCA的晶体结构^[93]（C1、C2、C3为原子序号）；(b) 顺式-FDCA纳米线的晶体结构^[93]

Figure 9. Crystal structures of (a) FDCA at 10.8 GPa^[93], in which C1, C2 and C3 are atom numbers, and (b) syn-FDCA nanothreads^[93]

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图 10 C₁₀H₈-C₁₀F₈共晶在(a) 15.9 GPa、(b)19.9 GPa和(c) 24.0 GPa时的单晶X射线衍射^[94]

Figure 10. Single crystal XRD of C₁₀H₈-C₁₀F₈ at (a) 15.9 GPa, (b)19.9 GPa and (c) 24.0 GPa^[94]

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图 11 (a) C₁₀H₈-C₁₀F₈共晶的晶体结构^[94]；(b) [4+2]环加成聚合路径^[94]；(c) “2A-tube”聚合路径^[94]；(d) Friedrich等^[95]提出的聚合路径

Figure 11. (a) Crystal structure of C₁₀H₈-C₁₀F₈^[94]; (b) the [4+2] cycloaddition polymerization path^[94]; (c) “2A-tube” polymerization path^[94]; (d) the polymerization path proposed by Friedrich et al.^[95]

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图 12 (a) DPB的反应示意图（RT代表室温）^[99]；(b) DPB在10 GPa下的晶体结构（D₁、D₂、D₃为原子间距）^[99]；(c) 相关反应的几何结构（1,4-加成反应中，R_1,4′为分子间1位和4′位炔碳原子之间的距离，D为取代基团（−R）之间的距离， $\varphi$ 为单体分子在堆积方向上的倾斜角）^[99] ；(d) GNR-1和GNR-2的结构模型^[99]

Figure 12. (a) Reaction diagram of DPB, in which RT represents room temperature^[99]; (b) crystal structure of DPB at 10 GPa, in which D₁、D₂、D₃ are the distances between atoms^[99]; (c) geometric structures of the relevant reactions ( In 1,4-addition reaction, R_1,4′ is the intermolecular distance between 1 and 4′ alkynyl carbon atoms, D is the distance between the substituent groups (−R), and $\varphi$ is the tilt angle of the monomer molecules in the stacking direction.)^[99] ; (d) structural models of GNR-1 and GNR-2^[99]

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图 13 (a) TEB的反应示意图^[100]；(b) 3.6 GPa时TEB的晶体结构^[100]；(c) 3.6 GPa时分子间C···C距离^[100]；(d) 纳米带模型^[100]

Figure 13. (a) Reaction diagram of TEB^[100]; (b) crystal structure of TEB at 3.6 GPa^[100]; (c) intermolecular C···C distance at 3.6 GPa^[100]; (d) nanoribbon models^[100]

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图 14 (a) 常压室温下偶氮苯的晶体结构^[105]；(b) 17.1 GPa时A层和B层中偶氮苯分子之间的距离^[105]（C1、C2′、C3、C4、C5、C6′、N1′、N2′为原子序号）；(c) A层偶氮苯通过HDA反应生成CNR-A和B层偶氮苯通过对聚反应生成CNR-B^[105]；(d) 聚偶氮苯的晶体结构^[105]

Figure 14. (a) Crystal structure of azobenzene at atmospheric pressure and room temperature^[105]; (b) the distance between azobenzene molecules in A and B layers at 17.1 GPa^[105], in which C1, C2′, C3, C4, C5, C6′, N1′ and N2′ are atom numbers ; (c) the A-layer azobenzene forms CNR-A by HDA reaction and the B-layer azobenzene forms CNR-B by para-polymerization reaction^[105] ; (d) crystal structure of polyazobenzene^[105]

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图 15 (a) 通过高分辨气相色谱-质谱联用技术在25 GPa回收的聚偶氮苯中检测到的主要低聚物及其含量^[105]；(b)同位素标记的低聚物的质谱和相应的分子结构（t代表保留时间）^[105]；(c) 通过高分辨气相色谱-质谱联用技术在物质的量的比为1∶1的C₁₂H₁₀N₂-C₁₂D₁₀N₂混合物的聚合产物中检测到H和D共标记的低聚物以及这些化合物与CNR-A/CNR-B的关系^[105]

Figure 15. (a) The main oligomers and their contents detected by HRGC-MS in polyazobenzene recovered from 25 GPa^[105]; (b) mass spectrum and corresponding molecular structures of isotopically labeled oligomers (t represents retention time)^[105]; (c) H and Dcolabeled oligomers detected by HRGC-MS in the polymerization products of mixture of C₁₂H₁₀N₂-C₁₂D₁₀N₂with a molar ratio of 1∶1 and the relationship between these compounds and CNR-A/CNR-B^[105]

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图 16 (a) 5.7 GPa下乙炔的晶体结构^[109]；(b) 10 GPa时顺式聚乙炔聚合成石墨烷的分子动力学模拟（PA代表顺式聚乙炔，PA后的数字代表计算的代数，10 GPa-PA-1代表10 GPa时计算得到的顺式聚乙炔结构）^[109]；(c) 样品P2的固态核磁共振^[109]；(d) 氘代样品P2的中子对分布函数的实验数据和动力学模拟的结构模型的对分布函数计算结果^[109]

Figure 16. (a) Crystal structure of ethyne at 5.7 GPa^[109]; (b) meta-dynamic simulation of the polymerization of cis-polyacetylene into graphane at 10 GPa (PA represents cis-PA, and the numbers following PA are the generation numbers. 10 GPa-PA-1 is the structure of cis-polyacetylene calculated at 10 GPa.)^[109]; (c) solid-state NMR of sample P2^[109]; (d) the neutron pair distribution function (PDF) experiment data of deuterated sample P2 and the calculated PDF of selected structural models of the dynamic simulations^[109]

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图 17 (a) 20 GPa时C₆D₆-C₆F₆共晶的晶体结构^[111]；(b) 从C₆D₆-C₆F₆共晶到H-F取代石墨烷的反应路线^[111]

Figure 17. (a) Crystal structure of C₆D₆-C₆F₆ at 20 GPa^[111]; (b) reaction route from C₆D₆-C₆F₆ to H-F-substituted graphane^[111]

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图 18 (a) 原料CaC₂以及通过巴黎-爱丁堡压机在26 GPa下合成的聚合产物的水解产物总离子色谱^[118]；(b) 30 GPa时分子动力学模拟的CaC₂结构^[118]

Figure 18. (a) Total ion chromatography of the raw material CaC₂ and the hydrolysis products of polymerization product synthesized by the Paris-Edinburgh cell at 26 GPa^[118]; (b) structure of CaC₂ simulated by meta-dynamics at 30 GPa^[118]

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图 19 (a) 高压下Li₂C₂的相变及反应过程^[119]；(b) Li₂C₂在高压下的理论和实验红外光谱^[119]；(c) 水解产物中各种碳氢化合物的相对含量以及化学计量比^[119]

Figure 19. (a) Phase transition and reaction process of Li₂C₂ under high pressure^[119]; (b) theoretical and experimental infrared spectra of Li₂C₂ under high pressure^[119]; (c) relative content and stoichiometry of hydrocarbons in the hydrolysis product^[119]

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图 20 (a) 准谐波近似（quasi-harmonic approximation ，QHA）理论计算得到的Li-C相图^[122]（n_Li/(n_Li+n_C)表示Li在Li-C化合物中的比例）；Li₂C₂在(b) 27.5GPa和(c) 36.5 GPa下的高温原位X射线粉末衍射谱^[122]；(d) 27.5 GPa、1696 K时LiC₂和(e) 36.5 GPa、2010 K时Li₃C₄的Rietveld精修结果^[122]

Figure 20. (a) Phase diagrams of Li-C calculated by quasi-harmonic approximation (QHA)^[122], in which n_Li/(n_Li+n_C) represents the proportion of Li in Li-C compound; in situ high temperature X-ray powder diffraction pattern of Li₂C₂ at (b) 27.5 GPa and(c) 36.5 GPa^[122]; rietveld refinement results of (d) LiC₂ at 27.5 GPa, 1696 K and (e) Li₃C₄ at 36.5 GPa, 2010 K^[122]

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图 21 (a) NaC₂H的高压反应示意图^[123]；(b) 临界压力下NaC₂H的晶体结构（d₁、d₂、d₃为原子间距^[123]）；(c)空气、NaC₂H以及20 GPa下回收样品的水解产物的总离子色谱、各组分的百分比以及与NIST谱的对比^[123]（m/z代表质荷比）；(d) 二聚及后续H转移过程的反应路线^[123]

Figure 21. (a) Diagram of high-pressure reaction of NaC₂H^[123]; (b) the crystal structure of NaC₂H under critical pressure^[123], in which d₁, d₂, d₃ are the distances between atoms; (c) total ion chromatography, percentages of each component and comparison with NIST spectrometry of air, raw materials and hydrolysates of samples recovered from 20 GPa^[123], in which m/z represents mass-to-charge ratio; (d) reaction route of dimerization and subsequent H-transfer process^[123]

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图 22 (a) 高压下 K₃Fe(CN)₆的晶格参数^[131]； (b) 1.7 GPa（左）和4.4 GPa（右）时K₃Fe(CN)₆的晶体结构和 ${\mathrm{Fe(CN)}} _6^{3-}$ 的局部结构^[133]；(c) 高压下K₃Fe(CN)₆的相变和化学反应过程^[133]

Figure 22. (a) Lattice parameters of K₃Fe(CN)₆ under high pressure^[131]; (b) the crystal structure of K₃Fe(CN)₆ and local structure of ${\mathrm{Fe(CN)}} _6^{3-}$ at 1.7 GPa (left) and 4.4 GPa (right)^[133]; (c) phase transition and chemical reaction process of K₃Fe(CN)₆ under high pressure^[133]

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图 23 Li₃Fe(CN)₆的晶体结构（棕色的八面体代表 ${\mathrm{Fe(CN)}} _6^{3-}$ ，紫色的原子代表Li⁺）^[134]

Figure 23. Crystal structure of Li₃Fe(CN)₆, in which the brown octahedron stands for ${\mathrm{Fe(CN)}} _6^{3-}$ and the purple atom stands for Li^+[134]

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图 24 (a) 20.6 GPa时CD₃CN的晶体结构模型以及可能的氢转移路线^[141]（C1、C2、D1、D2为原子序号）；(b) 通过分子动力学计算得到的35 GPa时乙腈的反应过程^[141]；(c) 乙腈在高压下的相变及聚合的示意图^[141]

Figure 24. (a) The crystal structure model of CD₃CN at 20.6 GPa and possible H-transfer routes^[141], in which C1, C2, D1, D2 are atom numbers; (b) the possible reaction process of acetonitrile at 35 GPa calculated by meta-dynamics^[141]; (c) diagram of phase transition and polymerization of acetonitrile under high pressure^[141]

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图 25 (a) 2-丁炔在高压下的氢转移过程（d₁为原子间距）^[142]；（b）密度泛函理论计算优化后的12.2 GPa时2-丁炔的晶体结构^[142]；(c) 化学键和弱相互作用的相互作用区域指示函数（interaction region indication，IRI）研究^[142]，IRI为1.1；(d) NEB计算中2-丁炔沿d₁的氢转移过程^[142]（C1、C1′、C2、C2′、H、H′为原子序号，NICS(1)_ZZ表示在6元环过渡态质心上方1 Å处环平面法向上的NICS投影）

Figure 25. (a) Hydrogen transfer diagram of 2-butylene^[142], in which d₁ is the distance between atoms; (b) the crystal structure of2-butylene at 12.2 GPa after DFT optimization^[142]; (c) interaction region indication (IRI) study of chemical bonds and weak interactions^[142], IRI equivalent is 1.1; (d) hydrogen transfer process of 2-butylene along d₁ in NEB calculation^[142] ( C1, C1′, C2, C2′, H and H′ are atom numbers. NICS(1)_ZZ represents NICS projection on the normal vector of the ring plane of the atom at 1 Å above mass center of the 6-member ring intermediate state.)

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表 1 不同反应体系中压力诱导聚合的分子间阈值距离

Table 1. Intermolecular threshold distances for pressure induced polymerization of different molecules

Molecules	d_{(C∙∙∙C)min}/Å	Reaction pressure/GPa	Functional group
Acetylene^[109]	3.1	5.7	Alkynyl
Acetylenedicarboxylic acid^[61]	3.1	8	Alkynyl
Monosodium acetylide^[123]	2.9	14	Alkynyl
Calcium acetylide^[118]	2.9	20	Alkynyl
Benzene^[37]	2.8	18	Phenyl
Benzene-hexafluorobenzene cocrystal^[111]	2.8	20	Phenyl
2,5-furandicarboxylic acid^[93]	2.8	11	Furan
Azobenzene-layer B^[105]	3.18	18	Phenyl
Azobenzene-layer A^[105]	3.0	18	Azo, phenyl
1,4-diphenylbutadiyne^[99]	3.2	10	Alkynyl, phenyl
1,3,5-triethynylbenzene^[100]	3.4	4	Alkynyl, phenyl

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