## 2 Results and Discussion
### Raman Studies on ZrO\({}_{2}\)@C, ZrC@C and (ZrC,ZrO\({}_{2}\))@C Composites
\begin{table}
\begin{tabular}{c c c c c c c c c c} \hline \hline
**Sample** & & **D \({}^{\star}\)** & **D** & **D\({}^{\prime\prime}\)** & **G** & **D\({}^{\prime}\)** & **2D** & **D + D\({}^{\prime}\)** & **ID/IG** & **I2D/IG** \\ \hline \multirow{4}{*}{L-Zr-Cl-1000-2-P-H\({}_{2}\)} & R shift & 1100 & 1340 & 1572 & 1592 & 1614 & 2676 & 2929 & \\  & [cm\({}^{-1}\)] & Intensity & 0 & 2650 & 1552 & 784 & 585 & 1313 & 173 & 3.38 & 1.68 \\  & FWHM & 0 & 53.53 & 44.38 & 29.40 & 23.47 & 71.72 & 40.98 & \\  & R shift & & 1100 & 1339 & 1488 & 1574 & 1603 & 2675 & 2930 & \\  & [cm\({}^{-1}\)] & Intensity & 0 & 1647 & 259 & 1012 & 705 & 305 & 110 & 1.63 & 0.30 \\  & FWHM & 0 & 81.88 & 115.5 & 52.17 & 35.59 & 79.04 & 54.11 & & \\  & R shift & & 1100 & 1340 & 1480 & 1574 & 1606 & 2680 & 2933 & \\  & [cm\({}^{-1}\)] & Intensity & 0 & 2762 & 206 & 2907 & 802 & 2070 & 157 & 0.95 & 0.71 \\  & FWHM & 0 & 57.92 & 88.54 & 40.51 & 29.73 & 60.06 & 35.56 & \\  & R shift & & 1100 & 1339 & 1481 & 1574 & 1607 & 2679 & 2933 & \\  & [cm\({}^{-1}\)] & Intensity & 0 & 2581 & 475 & 2670 & 1004 & 1343 & 178 & 0.97 & 0.50 \\  & FWHM & 0 & 80.57 & 109.4 & 46.94 & 30.00 & 62.47 & 57.14 & & \\  & R shift & & 1100 & 1339 & 1517 & 1582 & 2078 & 2671 & 2925 & \\ L-Zr-S-1000-2-P-H\({}_{2}\) & Intensity & 0 & 1943 & 60.55 & 1349 & 0 & 387 & 127 & 1.44 & 0.29 \\  & FWHM & 0 & 65.45 & 0.113 & 64.27 & 0 & 79.9 & 59.33 & & \\  & R shift & & 1100 & 1340 & 1494 & 1575 & 1604 & 2676 & 2934 & \\ L-Zr-S-1000-2-P-He & Intensity & 0 & 2128 & 392 & 1511 & 1068 & 558 & 143 & 1.41 & 0.37 \\  & FWHM & 0 & 97.33 & 109.5 & 51.36 & 35.97 & 80.13 & 75.83 & & \\ \hline \hline \end{tabular}
\end{table} 
Table 4: Raman shifts peak positions (in cm\({}^{-1}\)) and their intensities (in arbitrary units) for the plasma-treated samples. Figure 12: Raman spectra of plasma-treated L-Zr-X-P-H\({}_{2}\) samples (X=Cl, N and S). Figure 13: Raman spectra of plasma-treated L-Zr-X-P-He samples (X=CI, N and S). For the samples L-Zr-N-T-t, the catalytic effect of ZrC on graphitization might be more pronounced than the effect of temperature, whereas, for the L-Zr-S-t-t samples, the increase in temperature and reaction time resulted in regular improvements in the graphitization process (Supplementary Materials, Table S6). For the samples made from zirconyl nitrate, the ratio of amorphous carbon to graphite decreases with increasing temperature. The amorphous phase and polyenes completely disappear at 1400 \({}^{\circ}\)C in 2 h. Amorphous carbon remains in another experiment conducted at the same temperature but with a longer time (8 h). This shows that there are some differences between the two processes in terms of graphitization. This effect does not directly depend on heating time, but some other unknown factor(s), e.g., activation of some catalytic processes to increase nucleation or crystal growth, might play a role in its appearance. The Raman spectra of all plasma-treated samples show the complete disappearance of the D* bands due to the thermal decomposition of polyene structures and the transformation of surface graphene layers. The amount of defective graphite and amorphous carbon is the highest in the X=Cl sample made in H\({}_{2}\), and when the atmosphere was changed to He, the ID/IG and ID\"/(ID+G) ratios decreased from 0.45 to 0.097 and from 3.38 to 1.63, respectively. For the samples with X=N, the ID/IG and ID\"/(ID+G) ratios are close to each other. For the samples with X=N, less amorphous carbon is found, and the ratio of defective/regular graphitic structures is almost the same (ID/IG = 0.95 and 0.97 in H\({}_{2}\) and He, respectively). A considerable influence of the atmosphere in ABAB stacking and the separation of the monolayer sheets (I\({}_{2\mathrm{D}}\)/I\({}_{\mathrm{G}}\) ratio) was only found for the X=Cl sample [47; 48; 49].