Catalytic Combustion of Diesel Soot on Ce / Zr Series Catalysts Prepared by Sol-Gel Method

: Cerium-zirconium (Ce-Zr) solid solutions have been extensively used in a wide variety of catalytic processes due to their unique catalytic features in conjunction with lower cost compared to noble metal-based systems. A series of Ce-Zr-based catalysts was prepared by the sol-gel method. The structure and morphology of these catalysts were characterized by X-ray di ﬀ raction, thermogravimetric-di ﬀ erential scanning calorimetry, scanning electron microscopy, energy dispersive spectroscopy, and X-ray photoelectron spectroscopy. Furthermore, investigation on catalytic performance was carried out by constructing a test platform, and the result indicated that the catalysts apparently decreased the soot ignition temperature. These catalysts exhibited higher catalytic activity for soot oxidation under narrow contact conditions. The results revealed that some soot particles could react with adsorbed oxygen, and other part of diesel soot reacted with lattice oxygen. The activity of these catalysts was attributed to synergistic e ﬀ ect arising from the combination of K / Co / Zr and Ce-Zr solid solution, which led to the decrease in the ignition temperature to 294 ◦ C (data from the test platform). The catalyst still keeps good stability and catalytic activity after the cycle oxidation experiment. A reaction pathway was proposed to explain catalytic combustion process of soot, i.e., combination of K / Co / Zr with Ce-Zr solid solution reduced the binding energy of Ce-Zr solid solution, which was conducive to provide more active sites to release the active oxygen (O 2 − ) or lattice oxygen (O 2 − ). and these catalysts were tested in a platform to explore the catalytic properties towards soot particles. The results revealed that some soot particles could react with adsorbed oxygen, and other part of diesel soot could react with lattice oxygen. The remarkable catalytic performance, thermostability, and repetition stability of catalysts make them potential candidates for diesel emission control. Furthermore, a reaction pathway was proposed for comprehensive understanding of the catalytic oxidation of diesel soot using the as-fabricated catalysts. the and the temperature of the max oxidation rate of the particles signiﬁcantly The catalysts show excellent redox properties of Ce 3 + -Ce 4 + couple and active oxygen storage capacity, which can exchange oxygen in the gas phase. Compared to catalyst CZ and catalyst ZC, the atomic ratio of Ce 3 + / Ce 4 + of catalyst K / ZC is 0.13, it is obvious that the addition of K reduces the amount of Ce 3 + species and there are more oxygen vacancies in the catalyst system, allowing it to ignite the soot at a lower temperature. SEM images show that many small particles are deposited on the cobalt-doped catalyst (Co / CZ and Co / ZC), which can lead to a better contact of the catalyst with the soot, resulting a lower ignition temperature. The catalytic performance studies revealed that the Co / Ce 0.75 Zr 0.25 O 2 catalyst showed the lowest ignition temperature. The results revealed that some soot particles could react with adsorbed oxygen, and other part of diesel soot reacted with lattice oxygen. The activity of these catalysts is attributed to synergistic e ﬀ ect arising from the combination of K / Co / Zr and Ce-Zr solid solution, which leads to the decrease in ignition temperature to 294 ◦ C (data from the test platform). Furthermore, the reaction mechanism for the oxidation reactions of soot was proposed, combination of K / Co / Zr with Ce-Zr solid solution the binding energy of Ce-Zr solid which is conducive in providing more active sites to release the active oxygen (O 2 − ) lattice oxygen (O 2 − ). K structural


Introduction
Nowadays, humanity is facing various environmental problems, such as water pollution and air pollution, and a great number of researchers have reported different ways to treat contaminants [1][2][3][4]. Among them, the problem of air pollution is particularly prominent. Owing to the negative and hazardous environmental and health impacts of diesel particulate matter (PM) [5][6][7][8] and the necessity of complying with increasingly stringent automobile emissions regulations, significant research efforts to reduce PM emissions are ongoing, even though achievement of such reductions remains challenging [9]. PM is primarily composed of carbonaceous particles (also called soot), with diameters ranging from a few nanometers (10-20 nm) to several hundred nanometers [10]. These particles originate from incomplete in-cylinder oxidation of the fuel. Trapping of PM using a filter is an efficient way of eliminating this pollutant. In this approach, soot particles are separated from the gas phase by filtration through porous ceramic media. The particulates are accumulated in the channels of filter, pressure drop across the filter increases, and after some time, burning of soot particles accumulated inside  Figure 1a,c,e, ZC catalyst doped with K presents a different structure, which was more loose rather than dense, just as marked in red. Figure 1f present SEM images of Zr/ZC catalyst formed a layered structure. There are many small deposits presented on the large particles seen in Figure 1b,d. This means that small catalytic particles will achieve a closer contact with the soot, and we predict it may have a better catalytic performance.  Figure 1a,c,e, ZC catalyst doped with K presents a different structure, which was more loose rather than dense, just as marked in red. Figure 1f present SEM images of Zr/ZC catalyst formed a layered structure. There are many small deposits presented on the large particles seen in Figure 1b,d. This means that small catalytic particles will achieve a closer contact with the soot, and we predict it may have a better catalytic performance.   . The sol-gel method not only lowers the sintering temperature because it provides fine grains and homogeneous composition, but also makes the starting materials homogeneous according to the design stoichiometric ratio. One part of metal oxides was used to form CZ and ZC, and the other part of metal oxides was maintained in final product, in which coordination effect was caused on surface of catalysts to decrease the combustion temperature of soot.
Catalysts 2019, 9,   . The sol-gel method not only lowers the sintering temperature because it provides fine grains and homogeneous composition, but also makes the starting materials homogeneous according to the design stoichiometric ratio. One part of metal oxides was used to form CZ and ZC, and the other part of metal oxides was maintained in final product, in which coordination effect was caused on surface of catalysts to decrease the combustion temperature of soot.

Thermogravimetric-Differential Scanning Calorimetry Analysis of Soot
In order to display catalytic action, the thermal analysis of soot was carried out first under simulated automotive exhaust situation (10% oxygen and 90% nitrogen). The TG-DSC curve of soot is shown in Figure 3. Further, this result was used as a baseline to make comparison with the catalytic sample. The curve reveals that the mass loss occurs in a wide temperature range (497-681 °C), and two endothermic peaks appear simultaneously on the DSC curve. The ignition temperature of soot is 497

Thermogravimetric-Differential Scanning Calorimetry Analysis of Soot
In order to display catalytic action, the thermal analysis of soot was carried out first under simulated automotive exhaust situation (10% oxygen and 90% nitrogen). The TG-DSC curve of soot is shown in Figure 3.

Thermogravimetric-Differential Scanning Calorimetry Analysis of Soot
In order to display catalytic action, the thermal analysis of soot was carried out first under simulated automotive exhaust situation (10% oxygen and 90% nitrogen). The TG-DSC curve of soot is shown in Figure 3. Further, this result was used as a baseline to make comparison with the catalytic sample. The curve reveals that the mass loss occurs in a wide temperature range (497-681 °C), and two endothermic peaks appear simultaneously on the DSC curve. The ignition temperature of soot is 497 Further, this result was used as a baseline to make comparison with the catalytic sample. The curve reveals that the mass loss occurs in a wide temperature range (497-681 • C), and two endothermic peaks appear simultaneously on the DSC curve. The ignition temperature of soot is 497 • C and the maximum oxidation rate temperature is 603 • C, indicating that all the catalysts involved in the combustion of soot do not require higher temperature to stimulate soot combustion 2.1.4. Thermogravimetric-Differential Scanning Calorimetry Analysis of Samples So as to simply obtain the ignition temperature (T i ), the maximum oxidation rate temperature (T o ), and the burnout temperature (T b ) of mixture powders (soot + catalyst), the thermal analysis of mixture was carried out first under simulated automotive exhaust situation also. TG-DSC curves of mixture powders (soot + catalyst) are shown in Figure 4 and the T i , T o , and burnout temperature are listed in Table 1. So as to simply obtain the ignition temperature (Ti), the maximum oxidation rate temperature (To), and the burnout temperature (Tb) of mixture powders (soot + catalyst), the thermal analysis of mixture was carried out first under simulated automotive exhaust situation also. TG-DSC curves of mixture powders (soot + catalyst) are shown in Figure 4 and the Ti, To, and burnout temperature are listed in Table 1. It is well known that the CexZr1−xO2 solid solution exhibits higher activity than pure CeO2, and Ce0.69Zr0.31O2 (76 wt.% CeO2) [32] presents the lowest T50 value of 455 °C. In order to evaluate catalytic properties, the catalysts and diesel soot (PRINTEX-U) were mechanically mixed for 10 min to obtain the tight-contact (TC) mode. The results indicated significant decrease in the ignition temperature of soot under the action of these catalysts. In general, the ignition temperature of samples (catalyst + soot) decrease by 100-200 °C under the same testing condition compared to the sample without catalyst. Figure 4d,f exhibit the TG-DSC curves of two different Ce-Zr solid solutions, and results reveal that CZ exhibits better catalytic performance than ZC. Clearly, when Co3O4, ZrO2, and K2CeO3 It is well known that the Ce x Zr 1−x O 2 solid solution exhibits higher activity than pure CeO 2 , and Ce 0.69 Zr 0.31 O 2 (76 wt.% CeO 2 ) [32] presents the lowest T 50 value of 455 • C. In order to evaluate catalytic properties, the catalysts and diesel soot (PRINTEX-U) were mechanically mixed for 10 min to obtain the tight-contact (TC) mode. The results indicated significant decrease in the ignition temperature of soot under the action of these catalysts. In general, the ignition temperature of samples (catalyst + soot) decrease by 100-200 • C under the same testing condition compared to the sample without catalyst. Figure 4d,f exhibit the TG-DSC curves of two different Ce-Zr solid solutions, and results reveal that CZ exhibits better catalytic performance than ZC. Clearly, when Co 3 O 4 , ZrO 2 , and K 2 CeO 3 phases coexist with Ce x Zr 1−x O 2 solid solution, the ignition temperature of soot decreases and the catalytic performance of the catalyst gets improved as presented in Figure 4a-d. Among the catalysts, K/ZC exhibited an excellent effect and the ignition temperature was 351 • C, thus indicating that the oxidation of soot was promoted by increasing the catalyst contact with the high mobility alkali metals [15][16][17][18][19]. Figure 4e-f present the different between Cobalt-doped ZC (Co/CZ) and CZ. The Cobalt-doped ZC reduces the ignition temperature of the soot particles by 153 • C, and 17 • C lower compares to cat-CZ. This result is possibly attributed to the synergistic effect between Co 3 O 4 and Ce x Zr 1−x O 2 species. The distribution of Co influence the Ce x Zr 1−x O 2 crystallite particle size, the specific surface area, and the catalytic activity [33]. In summary, Ce-Zr solid solutions show good catalytic performance for soot combustion, and the Co/CZ (Co 3 O 4 /CZ) sample exhibits the best catalytic performance.

Samples or Soot
Ratio of Catalyst, Soot Atmosphere/%  Figure 5a shows the Ce 3d XPS spectra of cat-K/ZC, cat-CZ, and cat-ZC, which demonstrate the presence of eight components, as reported in several relevant studies [34][35][36][37][38][39][40][41]. The Ce 3d spectrum consists of two series of spin-orbit lines u and v. Figure 5a displays that Ce 3d 3/2 spin-obit components of cat-ZC which correspond to u lines include three characteristic peaks labeled as u (901.7 eV), u" (908.9 eV), and u Catalysts 2019, 9, x FOR PEER REVIEW phases coexist with CexZr1−xO2 solid solution, the ignition temperature o catalytic performance of the catalyst gets improved as presented in Figure 4a K/ZC exhibited an excellent effect and the ignition temperature was 351 C oxidation of soot was promoted by increasing the catalyst contact with the hi [15][16][17][18][19]. Figure 4e-f present the different between Cobalt-doped ZC (Co/C doped ZC reduces the ignition temperature of the soot particles by 153 C, a to cat-CZ. This result is possibly attributed to the synergistic effect betwe species. The distribution of Co influence the CexZr1−xO2 crystallite particle area, and the catalytic activity [33]. In summary, Ce-Zr solid solutio performance for soot combustion, and the Co/CZ (Co3O4/CZ) sample ex performance. XPS analysis was conducted to assess the impact of doping on elem shows the Ce 3d XPS spectra of cat-K/ZC, cat-CZ, and cat-ZC, which dem eight components, as reported in several relevant studies [34][35][36][37][38][39][40][41]. The Ce 3d series of spin-orbit lines u and v. Figure 5a displays that Ce 3d3/2 spin-ob which correspond to u lines include three characteristic peaks labeled as u and u‴ (917.0 eV). Ce 3d5/2 spin-orbit components which correspond to the three peaks labeled as v (883.1 eV), v" (889.7 eV), and v‴ (899.1 eV). These attributed to the characteristic peaks of Ce 4+ . Moreover, the residual two sp (903.7 eV) and v' (886.5 eV) belong to the Ce 3+ species. According to Lykaki characteristic peaks shift to the high binding area in our study, because o solid solution due to the addition of Zr to the crystal lattice of CeO2. Notew CZ are different from those of cat-K/ZC and cat-ZC. Ce 3d3/2 spin-obit com correspond to u line include three characteristic peaks labeled as u (902.2 e (917.0 eV). Ce 3d5/2 spin-orbit components which correspond to the series of peaks labeled as v (882.0 eV), v" (889.4 eV), and v‴ (899.1 eV). However, the 0.8 eV toward the low binding energy direction at u" (908.9 eV), which is c atomic ratio of Ce 3+ /Ce 4+ varies to 0.134 (K/ZC), 0.637 (CZ), 0.578 (ZC) afte K/ZC, it is obvious that the addition of K reduces the amount of Ce 3+ , t indicates that the Ce 4+ species is more than the Ce 3+ , therefore, there are mor catalyst system. The catalysts show excellent redox properties of Ce 3+ -Ce 4+ c storage capacity, which can exchange oxygen in the gas phase. Since the oxyg the oxygen in the gas phase into active oxygen, enhanced the oxidative prop the soot particles can be ignited at a lower temperature. phases coexist with CexZr1−xO2 solid solution, the ignition temperature of soot decreases and the catalytic performance of the catalyst gets improved as presented in Figure 4a-d. Among the catalysts, K/ZC exhibited an excellent effect and the ignition temperature was 351 C, thus indicating that the oxidation of soot was promoted by increasing the catalyst contact with the high mobility alkali metals [15][16][17][18][19]. Figure 4e-f present the different between Cobalt-doped ZC (Co/CZ) and CZ. The Cobaltdoped ZC reduces the ignition temperature of the soot particles by 153 C, and 17 C lower compares to cat-CZ. This result is possibly attributed to the synergistic effect between Co3O4 and CexZr1−xO2 species. The distribution of Co influence the CexZr1−xO2 crystallite particle size, the specific surface area, and the catalytic activity [33]. In summary, Ce-Zr solid solutions show good catalytic performance for soot combustion, and the Co/CZ (Co3O4/CZ) sample exhibits the best catalytic performance.  Figure 5a shows the Ce 3d XPS spectra of cat-K/ZC, cat-CZ, and cat-ZC, which demonstrate the presence of eight components, as reported in several relevant studies [34][35][36][37][38][39][40][41]. The Ce 3d spectrum consists of two series of spin-orbit lines u and v. Figure 5a displays that Ce 3d3/2 spin-obit components of cat-ZC which correspond to u lines include three characteristic peaks labeled as u (901.7 eV), u" (908.9 eV), and u‴ (917.0 eV). Ce 3d5/2 spin-orbit components which correspond to the series of v lines contain three peaks labeled as v (883.1 eV), v" (889.7 eV), and v‴ (899.1 eV). These three pairs of peaks are attributed to the characteristic peaks of Ce 4+ . Moreover, the residual two spectral lines labeled as u' (903.7 eV) and v' (886.5 eV) belong to the Ce 3+ species. According to Lykaki et al. [42], all these eight characteristic peaks shift to the high binding area in our study, because of the formation of Ce-Zr solid solution due to the addition of Zr to the crystal lattice of CeO2. Noteworthy, XPS spectra of cat-CZ are different from those of cat-K/ZC and cat-ZC. Ce 3d3/2 spin-obit components of cat-CZ which correspond to u line include three characteristic peaks labeled as u (902.2 eV), u" (910.9 eV), and u‴ (917.0 eV). Ce 3d5/2 spin-orbit components which correspond to the series of v lines contain the three peaks labeled as v (882.0 eV), v" (889.4 eV), and v‴ (899.1 eV). However, the peak for cat-K/ZC shifts 0.8 eV toward the low binding energy direction at u" (908.9 eV), which is caused by K doping. The atomic ratio of Ce 3+ /Ce 4+ varies to 0.134 (K/ZC), 0.637 (CZ), 0.578 (ZC) after calculated. For catalyst K/ZC, it is obvious that the addition of K reduces the amount of Ce 3+ , the decrease in the ratio indicates that the Ce 4+ species is more than the Ce 3+ , therefore, there are more oxygen vacancies in the catalyst system. The catalysts show excellent redox properties of Ce 3+ -Ce 4+ couple and active oxygen storage capacity, which can exchange oxygen in the gas phase. Since the oxygen vacancies can convert the oxygen in the gas phase into active oxygen, enhanced the oxidative properties of the catalyst. So, the soot particles can be ignited at a lower temperature.
(899.1 eV). These three pairs of peaks are attributed to the characteristic peaks of Ce 4+ . Moreover, the residual two spectral lines labeled as u' (903.7 eV) and v' (886.5 eV) belong to the Ce 3+ species. According to Lykaki et al. [42], all these eight characteristic peaks shift to the high binding area in our study, because of the formation of Ce-Zr solid solution due to the addition of Zr to the crystal lattice of CeO 2 . Noteworthy, XPS spectra of cat-CZ are different from those of cat-K/ZC and cat-ZC. Ce 3d 3/2 spin-obit components of cat-CZ which correspond to u line include three characteristic peaks labeled as u (902.2 eV), u" (910.9 eV), and u Catalysts 2019, 9, x FOR PEER REVIEW 6 phases coexist with CexZr1−xO2 solid solution, the ignition temperature of soot decreases an catalytic performance of the catalyst gets improved as presented in Figure 4a-d. Among the cata K/ZC exhibited an excellent effect and the ignition temperature was 351 C, thus indicating th oxidation of soot was promoted by increasing the catalyst contact with the high mobility alkali m [15][16][17][18][19]. Figure 4e-f present the different between Cobalt-doped ZC (Co/CZ) and CZ. The C doped ZC reduces the ignition temperature of the soot particles by 153 C, and 17 C lower com to cat-CZ. This result is possibly attributed to the synergistic effect between Co3O4 and CexZ species. The distribution of Co influence the CexZr1−xO2 crystallite particle size, the specific su area, and the catalytic activity [33]. In summary, Ce-Zr solid solutions show good cat performance for soot combustion, and the Co/CZ (Co3O4/CZ) sample exhibits the best cat performance.  [34][35][36][37][38][39][40][41]. The Ce 3d spectrum consists o series of spin-orbit lines u and v. Figure 5a displays that Ce 3d3/2 spin-obit components of c which correspond to u lines include three characteristic peaks labeled as u (901.7 eV), u" (908.9 and u‴ (917.0 eV). Ce 3d5/2 spin-orbit components which correspond to the series of v lines co three peaks labeled as v (883.1 eV), v" (889.7 eV), and v‴ (899.1 eV). These three pairs of peak attributed to the characteristic peaks of Ce 4+ . Moreover, the residual two spectral lines labeled (903.7 eV) and v' (886.5 eV) belong to the Ce 3+ species. According to Lykaki et al. [42], all these characteristic peaks shift to the high binding area in our study, because of the formation of C solid solution due to the addition of Zr to the crystal lattice of CeO2. Noteworthy, XPS spectra o CZ are different from those of cat-K/ZC and cat-ZC. Ce 3d3/2 spin-obit components of cat-CZ w correspond to u line include three characteristic peaks labeled as u (902.2 eV), u" (910.9 eV), a (917.0 eV). Ce 3d5/2 spin-orbit components which correspond to the series of v lines contain the peaks labeled as v (882.0 eV), v" (889.4 eV), and v‴ (899.1 eV). However, the peak for cat-K/ZC 0.8 eV toward the low binding energy direction at u" (908.9 eV), which is caused by K doping atomic ratio of Ce 3+ /Ce 4+ varies to 0.134 (K/ZC), 0.637 (CZ), 0.578 (ZC) after calculated. For ca K/ZC, it is obvious that the addition of K reduces the amount of Ce 3+ , the decrease in the indicates that the Ce 4+ species is more than the Ce 3+ , therefore, there are more oxygen vacancies catalyst system. The catalysts show excellent redox properties of Ce 3+ -Ce 4+ couple and active ox storage capacity, which can exchange oxygen in the gas phase. Since the oxygen vacancies can co the oxygen in the gas phase into active oxygen, enhanced the oxidative properties of the cataly s. The distribution of Co influence the CexZr1−xO2 crystallite particle size, the specific surface and the catalytic activity [33]. In summary, Ce-Zr solid solutions show good catalytic mance for soot combustion, and the Co/CZ (Co3O4/CZ) sample exhibits the best catalytic mance.  Figure 5a the Ce 3d XPS spectra of cat-K/ZC, cat-CZ, and cat-ZC, which demonstrate the presence of omponents, as reported in several relevant studies [34][35][36][37][38][39][40][41]. The Ce 3d spectrum consists of two of spin-orbit lines u and v. Figure 5a displays that Ce 3d3/2 spin-obit components of cat-ZC correspond to u lines include three characteristic peaks labeled as u (901.7 eV), u" (908.9 eV), ‴ (917.0 eV). Ce 3d5/2 spin-orbit components which correspond to the series of v lines contain peaks labeled as v (883.1 eV), v" (889.7 eV), and v‴ (899.1 eV). These three pairs of peaks are ted to the characteristic peaks of Ce 4+ . Moreover, the residual two spectral lines labeled as u' eV) and v' (886.5 eV) belong to the Ce 3+ species. According to Lykaki et al. [42], all these eight teristic peaks shift to the high binding area in our study, because of the formation of Ce-Zr olution due to the addition of Zr to the crystal lattice of CeO2. Noteworthy, XPS spectra of catdifferent from those of cat-K/ZC and cat-ZC. Ce 3d3/2 spin-obit components of cat-CZ which pond to u line include three characteristic peaks labeled as u (902.2 eV), u" (910.9 eV), and u‴ eV). Ce 3d5/2 spin-orbit components which correspond to the series of v lines contain the three labeled as v (882.0 eV), v" (889.4 eV), and v‴ (899.1 eV). However, the peak for cat-K/ZC shifts toward the low binding energy direction at u" (908.9 eV), which is caused by K doping. The ratio of Ce 3+ /Ce 4+ varies to 0.134 (K/ZC), 0.637 (CZ), 0.578 (ZC) after calculated. For catalyst it is obvious that the addition of K reduces the amount of Ce 3+ , the decrease in the ratio tes that the Ce 4+ species is more than the Ce 3+ , therefore, there are more oxygen vacancies in the st system. The catalysts show excellent redox properties of Ce 3+ -Ce 4+ couple and active oxygen (899.1 eV). However, the peak for cat-K/ZC shifts 0.8 eV toward the low binding energy direction at u" (908.9 eV), which is caused by K doping. The atomic ratio of Ce 3+ /Ce 4+ varies to 0.134 (K/ZC), 0.637 (CZ), 0.578 (ZC) after calculated. For catalyst K/ZC, it is obvious that the addition of K reduces the amount of Ce 3+ , the decrease in the ratio indicates that the Ce 4+ species is more than the Ce 3+ , therefore, there are more oxygen vacancies in the catalyst system. The catalysts show excellent redox properties of Ce 3+ -Ce 4+ couple and active oxygen storage capacity, which can exchange oxygen in the gas phase. Since the oxygen vacancies can convert the oxygen in the gas phase into active oxygen, enhanced the oxidative properties of the catalyst. So, the soot particles can be ignited at a lower temperature.   Figure 5b shows the Zr 3d XPS spectra of cat-K/ZC, cat-CZ, and cat-ZC; compared to the binding energy of Zr 3d 5/2 and Zr 3d 3/2 according to Handbook of the Elements and Native Oxides, the two characteristic peaks shift 2.8 eV toward the high binding energy. In a word, in Ce-Zr solid solution system, the electron density of outer layer of Ce and Zr increases. The incorporation of isovalent non-reducible elements, Zr 4+ ions, into a ceria lattice has a beneficial influence on the physicochemical and catalytic properties of Ce, improving its thermal stability, oxygen vacancies, and thus can significantly improve the catalytic activity.
The corresponding O 1s XPS spectra are illustrated in Figure 3c,  [42]. Zr exhibits a stable state in the catalyst system and can effectively prevent CeO 2 sintering at high temperatures. Ce and Zr form a stable Ce-Zr solid solution, which can enhance the oxygen storage capacity of Ce. Zr 4+ increases the electron density in the system, so the binding energy of O 1s shifts to high energy. Figure 5c clearly reveals that the peak area of adsorbed oxygen of cat-K/ZC is larger than that of cat-ZC and cat-CZ, which indicates more adsorption of oxygen on the surface of cat-K/ZC and easier catalysis of soot particles at a low temperature. Therefore, more soot reacted with adsorbed oxygen, and a higher concentration of CO 2 will be observed at 100-200 • C compared to cat-ZC, which will be discussed in after-mentioned catalytic performance (Section 2.2.). For three samples, the following order, in terms of the O I / O II ratio, is obtained, K/ZC (5.64) > CZ (4.20) > ZC (4.03), which is perfectly matched to the order of their catalytic performance, as discussed above. These findings along with the TG-DSC results corroborate that the sample with a loose particles, named cat-K/ZC, demonstrate a higher population of loosely bound oxygen species, resulting in improved reducibility. It must be pointed out that the doped-K reduced the electron density of system because the outer electrons number of K less than Ce and Zr, so the binding energy shift to high energy less than 0.6 eV compared to cat-CZ. Figure 6 exhibits the SEM and EDS results of K/ZC after two cycles and five cycles, respectively. And the elemental ratio (wt%) in K/ZC compositions as per the EDS data was listed in Table 2. Morphological characterization by SEM shows that catalyst K/ZC is irregular in shape, which originated from aggregation of nano-particles. K/ZC particles increase the degree of aggregation after five catalytic cycles. Table 2 shows that the catalyst has a stable elemental composition. Even after five cycles of testing, the elemental content of the catalyst still keeps good stability.    Figure 4) that these catalysts also has a small amount of weight loss, meaning a little soot was burned at 100-200 °C, this value of weight loss is 1%-2%. As can be seen from Figure 7b-1, the amount of CO2 released by the catalyst K/ZC at 100-200 °C is significantly more than catalyst CZ and catalyst ZC, which is consistent with the results obtained in Figure 5c. This result prove that there is more adsorption of oxygen on the surface of cat-K/ZC and can easier catalyze more soot particles at a low temperature, just as seen in Figure 5c, the peak area of adsorbed oxygen (OII) of cat-K/ZC is larger than that of cat-ZC and cat-CZ. In contrast, a large amount of CO2 is detected in the temperature range from 300-400 °C, which is ascribed to the reaction of lattice oxygen (Olat) in the catalysts with soot, thus releasing CO2. Concentration of CO2 exhibits relationship with the oxygen concentration, i.e. the sum of the CO2 concentration and the O2 concentration is a constant value related to the incoming O2 concentration. This indicates that the CO2 concentration curve and the O2 concentration curve are complementary.   Figure 4) that these catalysts also has a small amount of weight loss, meaning a little soot was burned at 100-200 • C, this value of weight loss is 1%-2%. As can be seen from Figure 7b-1, the amount of CO 2 released by the catalyst K/ZC at 100-200 • C is significantly more than catalyst CZ and catalyst ZC, which is consistent with the results obtained in Figure 5c. This result prove that there is more adsorption of oxygen on the surface of cat-K/ZC and can easier catalyze more soot particles at a low temperature, just as seen in Figure 5c, the peak area of adsorbed oxygen (O II ) of cat-K/ZC is larger than that of cat-ZC and cat-CZ. In contrast, a large amount of CO 2 is detected in the temperature range from 300-400 • C, which is ascribed to the reaction of lattice oxygen (O lat ) in the catalysts with soot, thus releasing CO 2 . Concentration of CO 2 exhibits relationship with the oxygen concentration, i.e., the sum of the CO 2 concentration and the O 2 concentration is a constant value related to the incoming O 2 concentration. This indicates that the CO 2 concentration curve and the O 2 concentration curve are complementary. The CO2 concentration curves are close to trapezoidal shape, while the oxygen concentration is 6%, 8%, 10%, 12%, and 14%. This is a hysteresis effect which indicates that the soot particles could not burn out in an insufficient oxygen situation. Irrespective of the catalyst tested under test conditions with a same oxygen concentration of 10%, the highest concentration of CO2 was almost the same, which confirms that the oxygen concentration limits the highest concentration of CO2. Figure 7b-1 demonstrates that the ignition temperatures of the diesel soot mixed with catalysts decrease apparently, the catalyst Co/ZC shows the lowest ignition temperature (294.2 °C), and the catalyst ZC exhibits the highest ignition temperature (338.5 °C). The curves for CO2 concentration in case of Co/CZ present a trapezoidal shape, and that for catalyst ZC with the highest ignition temperature is triangular shape. The soot is rapidly oxidized and burned to CO2 which removes most of the lattice oxygen of the catalyst. As the oxygen is continuously ventilated and the temperature increases, the catalyst is reactivated and continues to catalyze and oxidize the remaining soot. At higher temperatures, the catalyst can simultaneously catalyze the soot and reactivate with the oxygen. This process occurs almost simultaneously, thus the curve shows a triangular shape.

Analysis of Catalytic Performance
The soot combustion parameters (O2 concentration, ignition temperature, maximum oxidation rate temperature, etc.) are listed in Table 3. In the simulation exhaust condition (10% O2), catalyst Co/CZ acquires the lowest ignition temperature (294.2 °C) and catalyst Zr/ZC shows the lowest burnout temperature (403.3 °C). In a word, the incoming O2 concentration has important influence on ignition temperature and burnout temperature. Jing X et al. studied spinel-type PdxCo3−xO4 binary active sites on 3D ordered meso-macroporous Ce-Zr-O2 for catalytic soot oxidation. Its T10 value is 313°C [29], higher than the catalyst Co/CZ. Furthermore, catalyst doping with Pt is more expensive too. The CO 2 concentration curves are close to trapezoidal shape, while the oxygen concentration is 6%, 8%, 10%, 12%, and 14%. This is a hysteresis effect which indicates that the soot particles could not burn out in an insufficient oxygen situation. Irrespective of the catalyst tested under test conditions with a same oxygen concentration of 10%, the highest concentration of CO 2 was almost the same, which confirms that the oxygen concentration limits the highest concentration of CO 2 . Figure 7b-1 demonstrates that the ignition temperatures of the diesel soot mixed with catalysts decrease apparently, the catalyst Co/ZC shows the lowest ignition temperature (294.2 • C), and the catalyst ZC exhibits the highest ignition temperature (338.5 • C). The curves for CO 2 concentration in case of Co/CZ present a trapezoidal shape, and that for catalyst ZC with the highest ignition temperature is triangular shape. The soot is rapidly oxidized and burned to CO 2 which removes most of the lattice oxygen of the catalyst. As the oxygen is continuously ventilated and the temperature increases, the catalyst is reactivated and continues to catalyze and oxidize the remaining soot. At higher temperatures, the catalyst can simultaneously catalyze the soot and reactivate with the oxygen. This process occurs almost simultaneously, thus the curve shows a triangular shape.
The soot combustion parameters (O 2 concentration, ignition temperature, maximum oxidation rate temperature, etc.) are listed in Table 3. In the simulation exhaust condition (10% O 2 ), catalyst Co/CZ acquires the lowest ignition temperature (294.2 • C) and catalyst Zr/ZC shows the lowest burnout temperature (403.3 • C). In a word, the incoming O 2 concentration has important influence on ignition temperature and burnout temperature. Jing X et al. studied spinel-type Pd x Co 3−x O 4 binary active sites on 3D ordered meso-macroporous Ce-Zr-O 2 for catalytic soot oxidation. Its T 10 value is 313 • C [29], higher than the catalyst Co/CZ. Furthermore, catalyst doping with Pt is more expensive too. Compared to other researchers' studies, catalyst Co/CZ and Co/ZC have a better catalytic performance. We list the ignition temperature (T i ) (or temperature at 10% of soot conversion (T 10 )) and the temperature of the max oxidation rate (T o ) (or temperature at 50% of soot conversion (T 50 )) of these catalysts in Table 4. Compared to these data from Table 4, Pt [43], Au [44], and Cu [45] doped in a catalyst all have an excellent performance. Among them, Au-doped catalyst has the best effect, but the high cost limits it's widely applications. The cobalt-doped Ce-Zr solid solution catalysts have better catalytic effect than other catalysts and has great application prospects because of highly efficient and economical.  [45] 368 472 Cu 0.9 Ce 0.05 Zr 0.05 O 2-δ [45] 284 468 It's reported that alkali metal doping may cause catalyst poisoning and deactivation [46][47][48]. Therefore, it's necessary to evaluate the cyclic stability of the catalyst which was doped with alkali metal. Thus, K/ZC was selected as a representative specimen to carry out the cyclic stability experiment in this study. Concentration of gases was measured directly through the testing platform to confirm some parameters of soot catalytic combustion, and the corresponding curves are shown in Figure 8. In the first catalytic cycle, T i (307.5 • C) and T o (324.2 • C) are different from others cycles. A reasonable explanation is that catalyst K/ZC maintains active framework via the sol-gel preparation and these active sites can accelerate catalytic combustion at lower temperature. However, the active site gets destroyed after the first soot combustion process and the catalyst acquires the stable state, thus T i and T o (from the second cycle to the fifth cycle) have almost the same value. It can be seen from the SEM (Figure 6) that the microstructure of the catalyst K/ZC is very stable after two cycles and five cycles. Moreover, the content of each element of the catalyst keeps a stable value, from the results of EDS. Through this sustainable repeated experiment, it was confirmed that the K/ZC catalyst possesses good structural stability and catalytic performance stability, which has an important application in soot combustion field. In all XRD showed that the catalysts prepared by the sol-gel method have good crystallinity. SEM characterization results showed that many small catalyst particles are deposited on the Codoped catalyst, which get a closer contact with the soot. And the soot was been ignited in a lower temperature, which was demonstrated by platform testing. The TG-DSC analysis and platform testing showed that the Ce-Zr solid solution catalyst can effectively reduce the ignition temperature and the temperature of the max oxidation rate of soot particles. Doping different metals (K, Zr, Co) in the Ce-Zr solid solution system can make the ignition temperature of soot particles reduced more. EDS exhibited that the elemental mass percentage of catalyst kept a stable value after two cycles and five cycles. Even after five cycles of experiments, the catalyst still had a stable structure showing good stability, which is along the results from the platform test.
The present findings can be rationalized based on Mars-van Krevelen redox-type mechanism, well documented in literature reports [49][50][51][52][53], and the catalyst reaction process is shown in Figure 9. When the catalyst is in contact with the soot, the exhaust gas provides a high temperature environment so that the soot can take away the lattice oxygen in the catalyst. Several reaction steps take place as follows, (i) The lattice oxygen in catalyst reacts very easily with soot towards the formation of active species. (ii) The lattice oxygen in the catalyst reacts with active species to form CO2 (iii) Oxygen is supplied to the catalyst during continuous aeration, filling the oxygen deficiency in the catalyst, and thus the catalyst is regenerated. In all XRD showed that the catalysts prepared by the sol-gel method have good crystallinity. SEM characterization results showed that many small catalyst particles are deposited on the Co-doped catalyst, which get a closer contact with the soot. And the soot was been ignited in a lower temperature, which was demonstrated by platform testing. The TG-DSC analysis and platform testing showed that the Ce-Zr solid solution catalyst can effectively reduce the ignition temperature and the temperature of the max oxidation rate of soot particles. Doping different metals (K, Zr, Co) in the Ce-Zr solid solution system can make the ignition temperature of soot particles reduced more. EDS exhibited that the elemental mass percentage of catalyst kept a stable value after two cycles and five cycles. Even after five cycles of experiments, the catalyst still had a stable structure showing good stability, which is along the results from the platform test.
The present findings can be rationalized based on Mars-van Krevelen redox-type mechanism, well documented in literature reports [49][50][51][52][53], and the catalyst reaction process is shown in Figure 9. When the catalyst is in contact with the soot, the exhaust gas provides a high temperature environment so that the soot can take away the lattice oxygen in the catalyst. Several reaction steps take place as follows, (i) The lattice oxygen in catalyst reacts very easily with soot towards the formation of active species. (ii) The lattice oxygen in the catalyst reacts with active species to form CO 2 (iii) Oxygen is supplied to the catalyst during continuous aeration, filling the oxygen deficiency in the catalyst, and thus the catalyst is regenerated. This reaction mechanism can be used to explain why the CO2 concentration curve of Co/CZ catalyst presents a trapezoidal shape and that of ZC catalyst presents a triangular shape as presented in Figure 8b-1. When the temperature reaches the temperature of the maximum oxidation rate, the soot is rapidly oxidized and burned to CO2 which depletes most of the lattice oxygen of catalysts. As the oxygen is continuously ventilated and the temperature increases, catalysts reactivate and continue to catalyze and oxidize the remaining soot. Further, the soot burns catalytically with the oxygen, thus it shows a triangular shape as presented in Figure 8b-1. The catalyst is cycled back and forth to complete the regeneration process. The doped (K, Co, Zr) catalyst shows larger oxygen vacancy, so that it can catalyze the soot at lower temperature.

Materials Preparation
A series of catalysts was prepared by the citric acid sol-gel method using metal nitrate precursors. Cobalt nitrate hexahydrate (Co(NO3)2·6H2O, AR, Kermel Chemical Reagent Co. Tianjin, , China), cerium nitrate hexahydrate (Ce(NO3)3·6H2O, AR, Shanpu Chemical Reagent Co. Shanghai, state abbrev if USA, China), zirconium nitrate pentahydrate (Zr(NO3)4·5H2O, AR, Kermel Chemical Reagent Co.), potassium nitrate (KNO3, AR, Hongyan chemical reagent Co.) and citric acid (C6H8O7, AR, Huada Chemical Reagent Co. Changzhou, state abbrev if USA, China) were used as raw materials in the present study. Firstly, Ce (NO3)3·6H2O (3.256 g, 7.5 mmol) was dissolved in 20 mL deionized water, and a solution of Zr(NO3)4·5H2O (1.073 g, 2.5 mmol) in 20 mL was added. The mixture was stirred for 20 min at room temperature, and then mixed with citric acid solution which was equal to the total moles of Ce (NO3)3·6H2O and Zr(NO3)4·5H2O. The resulting amaranthine solution was stirred continuously at 85 °C for 1.5 h holding time, and the mixture solution gradually transformed into a viscous gel. After that, the wet gel was dried at 110 °C in the furnace for 48 h, and the loose purple powder was obtained after grinding treatment. Finally, the powder was heated from room temperature to 600 °C for 5 h sintering in muffle furnace, the sample of Ce0.75Zr0.25O2 (named CZ) was obtained. According to the similar fabrication processes, Zr0.84Ce0.16O2 (named ZC) was formed controlling Zr/Ce molar ratio to be 21,4, zirconium-riched Zr0.84Ce0.16O2 (named Zr/ZC) was prepared controlling Zr/Ce molar ratio to be 21,2, potassium-doped Zr0.84Ce0.16O2 (named K/ZC) was prepared controlling K, Zr, Ce to be 21,4,4, cobalt-doped Zr0.84Ce0.16O2 (named Co/ZC) was formed controlling Co, Zr, Ce to be 21,4,4, and cobalt-doped Ce0.75Zr0.25O2 (named Co/CZ) was fabricated controlling Co, Ce, Zr to be 3,3,1. This reaction mechanism can be used to explain why the CO 2 concentration curve of Co/CZ catalyst presents a trapezoidal shape and that of ZC catalyst presents a triangular shape as presented in Figure 8b. When the temperature reaches the temperature of the maximum oxidation rate, the soot is rapidly oxidized and burned to CO 2 which depletes most of the lattice oxygen of catalysts. As the oxygen is continuously ventilated and the temperature increases, catalysts reactivate and continue to catalyze and oxidize the remaining soot. Further, the soot burns catalytically with the oxygen, thus it shows a triangular shape as presented in Figure 8b. The catalyst is cycled back and forth to complete the regeneration process. The doped (K, Co, Zr) catalyst shows larger oxygen vacancy, so that it can catalyze the soot at lower temperature.

Materials Preparation
A series of catalysts was prepared by the citric acid sol-gel method using metal nitrate precursors.

Characterization
X-ray diffraction (XRD) patterns of the samples were obtained with an AXS D8 Advance diffractometer (Bruker, Germany) with Cu Kα radiation (0.154 nm) operating at 40 kV and 30 mA. The XRD patterns were recorded in the 2 • range of 10 • -80 • with a scanning rate of 10 • /min. The morphology of the samples were observed by field-emission scanning electron microscopy (S-4800, Hitachi, Tokyo, Japan) with a 10 kV operating voltage. The energy dispersive spectrometer (EDS) of the samples were observed by field-emission scanning electron microscopy (Quanta 600F, FEI, Hillsboro, OR, USA) attached to an a EDS (INCA-350, Oxford Instruments, Oxfordshire, UK). Thermal analysis was performed in a simultaneous thermogravimetry and differential scanning calorimetry (TG-DSC) (STA 449F5, Netzsch, Selb, Germany). The thermal analysis of samples was carried out under simulated automotive exhaust situation (10% oxygen and 90% nitrogen, 100 mL/min) (from 50 • C to 600 • C, 10 • C/min). The X-ray photoelectron spectroscopy (XPS) was recorded on a PHI quantera II instrument (ULVAC, Japan) under ultra-high vacuum using a monochromated Al Kα source (1486.6 eV) at 42.1 W. The measurements were performed at 20 eV pass energy, 0.1 eV step and 0.15 min dwelling time.

Catalytic Properties
Schematic illustration of soot combustion test platform is shown in Figure 10. A mass flow controller is used to control the experimental atmosphere. A tubular muffle furnace is used for programmed heating of samples. Gases concentration data through exhaust gas analyser record by computer. The catalysts and diesel soot were mechanically mixed in tight-contact (TC) and then the mixture was placed into tubular muffle furnace. First, using N 2 to remove the exhaust gas, and the catalyst was mixed with carbon black particles (PRINTEX-U) in 10:1 ratio. Then, the mixture (0.55 g) was accurately weighed and placed in a quartz tube. Subsequently, input mass flow of gases was controlled to simulate the diesel engine exhaust and gases concentration data through exhaust gas analyser and muffle furnace heating temperature were recorded.

Catalytic Properties
Schematic illustration of soot combustion test platform is shown in Figure 10. A mass flow controller is used to control the experimental atmosphere. A tubular muffle furnace is used for programmed heating of samples. Gases concentration data through exhaust gas analyser record by computer. The catalysts and diesel soot were mechanically mixed in tight-contact (TC) and then the mixture was placed into tubular muffle furnace. First, using N2 to remove the exhaust gas, and the catalyst was mixed with carbon black particles (PRINTEX-U) in 10,1 ratio. Then, the mixture (0.55 g) was accurately weighed and placed in a quartz tube. Subsequently, input mass flow of gases was controlled to simulate the diesel engine exhaust and gases concentration data through exhaust gas analyser and muffle furnace heating temperature were recorded. In order to evaluate the cyclic stability of the catalyst, K/ZC was selected as a specimen to carry out cyclic stability experiment in this study. After different cycle times, catalysts were characterized by SEM and EDS for research on microstructural stability and composition stability.

Conclusions
Remarkable catalytic performance, thermostability, and repetition stability of catalysts (K/Zr0.84Ce0.16O2, Zr/Zr0.84Ce0.16O2, Co/Zr0.84Ce0.16O2, Zr0.84Ce0.16O2, Co/Ce0.75Zr0.25O2, and Ce0.75Zr0.25O2) prepared by sol-gel method make it possible to use these catalysts in diesel emission control. In the Ce-Zr solid solution system, Zr increase the oxygen storage capacity of Ce and prevent cerium oxide from sintering at high temperatures. The incorporation of isovalent non-reducible elements, Zr 4+ ions, into a ceria lattice has a beneficial influence on the physicochemical and catalytic properties of Ce, improving its thermal stability, oxygen vacancies, and thus can significantly improve the catalytic activity. By doping different elements (Co, Zr, and K), the ignition temperature and the temperature of the max oxidation rate of the soot particles can be significantly reduced. The catalysts show excellent redox properties of Ce 3+ -Ce 4+ couple and active oxygen storage capacity, which can In order to evaluate the cyclic stability of the catalyst, K/ZC was selected as a specimen to carry out cyclic stability experiment in this study. After different cycle times, catalysts were characterized by SEM and EDS for research on microstructural stability and composition stability.

Conclusions
Remarkable catalytic performance, thermostability, and repetition stability of catalysts (K/Zr 0.84 Ce 0. 16  ) prepared by sol-gel method make it possible to use these catalysts in diesel emission control. In the Ce-Zr solid solution system, Zr increase the oxygen storage capacity of Ce and prevent cerium oxide from sintering at high temperatures. The incorporation of isovalent non-reducible elements, Zr 4+ ions, into a ceria lattice has a beneficial influence on the physicochemical and catalytic properties of Ce, improving its thermal stability, oxygen vacancies, and thus can significantly improve the catalytic activity. By doping different elements (Co, Zr, and K), the ignition temperature and the temperature of the max oxidation rate of the soot particles can be significantly reduced. The catalysts show excellent redox properties of Ce 3+ -Ce 4+ couple and active oxygen storage capacity, which can exchange oxygen in the gas phase. Compared to catalyst CZ and catalyst ZC, the atomic ratio of Ce 3+ /Ce 4+ of catalyst K/ZC is 0.13, it is obvious that the addition of K reduces the amount of Ce 3+ species and there are more oxygen vacancies in the catalyst system, allowing it to ignite the soot at a lower temperature. SEM images show that many small particles are deposited on the cobalt-doped catalyst (Co/CZ and Co/ZC), which can lead to a better contact of the catalyst with the soot, resulting a lower ignition temperature. The catalytic performance studies revealed that the Co/Ce 0.75 Zr 0.25 O 2 catalyst showed the lowest ignition temperature. The results revealed that some soot particles could react with adsorbed oxygen, and other part of diesel soot reacted with lattice oxygen. The activity of these catalysts is attributed to synergistic effect arising from the combination of K/Co/Zr and Ce-Zr solid solution, which leads to the decrease in ignition temperature to 294 • C (data from the test platform). Furthermore, the reaction mechanism for the oxidation reactions of soot was proposed, combination of K/Co/Zr with Ce-Zr solid solution reduces the binding energy of Ce-Zr solid solution, which is conducive in providing more active sites to release the active oxygen (O 2 − ) or lattice oxygen (O 2− ). It is thus proved that the K/ZC catalyst possesses good structural stability and catalytic performance stability as indicated by the catalyst stability experiment, and thus shows potential application prospects for effective removal of diesel soot. In a word, these high efficient, long life period and economical catalyst make it possible to use for combustion of diesel soot.