Construction of stabilized bulk-nano interfaces for highly promoted inverse CeO2/Cu catalyst

As the water-gas shift (WGS) reaction serves as a crucial industrial process, strategies for developing robust WGS catalysts are highly desiderated. Here we report the construction of stabilized bulk-nano interfaces to fabricate highly efficient copper-ceria catalyst for the WGS reaction. With an in-situ structural transformation, small CeO2 nanoparticles (2–3 nm) are stabilized on bulk Cu to form abundant CeO2-Cu interfaces, which maintain well-dispersed under reaction conditions. This inverse CeO2/Cu catalyst shows excellent WGS performances, of which the activity is 5 times higher than other reported Cu catalysts. Long-term stability is also very solid under harsh conditions. Mechanistic study illustrates that for the inverse CeO2/Cu catalyst, superb capability of H2O dissociation and CO oxidation facilitates WGS process via the combination of associative and redox mechanisms. This work paves a way to fabricate robust catalysts by combining the advantages of bulk and nano-sized catalysts. Catalysts with such inverse configurations show great potential in practical WGS applications.

When comparing the inverse catalyst with the supported Cu the composition of both catalysts is very different (10.7 wt% as opposed to 82.9 wt% in the inverse system). How do the different rates of both systems compare in terms of specific surface area and the metal loading. (rates are stated/compared per gram only). The authors claim that the perimeter between the oxide particle and the Cu is responsible but this remains elusive as it could not be quantified for both catalysts. It appears that the Cu supported on CeO2 remains oxidized also under WGS and reducing atmosphere. Could this also be an explanation for the lower observed activity? On page 10 the authors state "we have further confirmed that for inverse CeO2/Cu catalyst, metallic Cu is the only active phase detected for WGS". Shouldn't this hold true for the "normal" catalyst and be an explanation for the reduced activity? In table 1 on page 6 BET surface areas are stated but it is not clear whether they were measured before or after catalysis. The sintering of the Cu particles in case of the inverse system is severe and should be accounted for. When the authors state "after catalysis" a time on stream should be stated as structural changes might be related to this time. On page 5 when discussing the (apparent) activation barriers the error should be stated. The finding that the Ea for the "normal" Cu/CeO2 catalyst was 3.7 kJ/mol lower might well be within error margins. On page 8 when discussing the number of defects (Ce3+) the authors state that the dominant species was Ce4+. This is unexpected as the higher activity of the inverse system is usually ascribed to a higher fraction of Ce3+ as the active site for H2O dissociation. Did the authors also try methods such as Raman spectroscopy to quantify? When discussing the in-situ experiments (depicted in Figure 4) the authors postulate, however, such defect sites. (see also the above mentioned publications) In Figure 4, regarding the DRIFTS measurements: It appears that the spectra only contain information from the gas phase (namely CO2). Also the experimental conditions, i.e. the water content was much lower. I would have expected to see water and as the case may be OH from the oxide surface. What could be an explanation? At current I don't see why the DRIFTS contain any additional information than the formation of CO2 in the gas phase?
Reviewer #3 (Remarks to the Author): In this manuscript, the authors report on the preparation of an inverse catalyst consisting of rather large Cu nanoparticles that serve as a support for much smaller CeO2 nanoparticles. Interestingly, such structures appear to show good activity and stability for the water-gas shift (WGS) reaction. With some small exceptions, the authors appear to have done a relatively thorough job in characterizing both the initial structure of the catalyst as well as the final structure under reaction conditions. (The final structure is very different from the initial structure, due to a very large extent of Cu sintering.). Overall, this concept of using relatively large Cu particles as supports for CeO2 particles is an interesting one, though I do have a few comments for this manuscript: Did the authors determine the uncertainties based on replicate experiments for the results in Figure 1? It does not seem clear from the methods section. Showing meaningful uncertainty analysis is especially important for justifying the claim that the inverse CeO2/Cu catalyst has higher activity at long times than does that commercial WGS catalyst. In general, there seems to be a lack of sufficient error analysis in the manuscript.
My other major comments is that the paper would be significantly improved if the authors could demonstrate that the reaction rate on their inverse system is proportional to some measure of the number of interfacial sites. Based on their characterization results and the cartoon pictured in Figure  1(h), can the authors estimate the interfacial areas for some of the catalysts shown in Supplementary figure 1, and perhaps demonstrate that the reaction rate scales with perimeter around the CeO2 nanoparticles?
It is a little unclear on page 5 when the authors report an activation energy of 37.1 kJ/mol for the inverse catalyst and that Cu-CeO2 is 3.7 kJ/mol higher. The authors then say Cu-CeO2 is expected to be close to 50-60 kJ/mol. Can they explain this apparent discrepancy?
Is it surprising that the CeO2 shows no chemical shifts as the Cu loading increases in Figure S4? Also, is there some reason that the Ce intensity does not appear to change over most of the range of bulk composition changes?
Can the authors comment on how the Cu surface areas / particle sizes compare between the catalyst reported here, the supported Cu/CeO2 catalyst, and the Cu-Zn-Al catalyst?

Responses to the reviewers' comments
Based on the above, I do not recommend publication.
Author Reply: The reviewer's kind comment on our work is highly appreciated. We found that our former mechanism study was incomplete and not very deep. The reviewer makes a great point saying associative mechanism is more efficient at the metal/oxide interface. In fact, recently, by using in-situ DRIFTS and TPSR, our group has also proved that associative mechanism is dominant at the Au-CeO 2 interface (Fu X. et al. J. Am. Chem. Soc. 2019, 141, 4613). According to the constructive criticism on the mechanism study, we have carefully read the literatures that the reviewer listed and re-designed our experiments. As mentioned by the reviewer, the DRIFTS signal of CO was not detected under WGS conditions. However, we did the DRIFTS measurements just to examine the CO adsorption, although no adsorbed CO was detected, not for exploring the mechanism. Here, we have carefully re-designed the TPSR experiments to examine the reaction mechanism. The results proved the inverse CeO 2 /Cu catalyst followed a combination of associative mechanism and redox mechanism. As the reviewer's comment said, associative mechanism should not be ruled out for the inverse catalyst. The detailed results were described as follows: Following the associative mechanism, quantified measurement of CO 2 and H 2 concentration in TPSR must give the ratio of 2:1 (Fu X. et al. J. Am. Chem. Soc. 2019, 141, 4613), since 2 CO molecules reacted with 2 −OH to generate 2 CO 2 molecules and 1 H 2 (2CO + 2−OH → 2CO 2 + H 2 ). In the former manuscript, the catalyst was firstly reduced by H 2 and then introduced to H 2 O, which was not real WGS condition. Such treatment led to oxidation of Cu by H 2 O, causing exorbitant CO 2 : H 2 ratio of 10 : 1, which was much higher than 2 : 1.
Therefore, in our original manuscript, combining that H 2 was generated through the disassociation of H 2 O on CeO 2 /Cu without the presence of CO, we thought the WGS catalyzed by the inverse CeO 2 /Cu followed the redox mechanism. Now we have found that such a process was not proper to reflect the real status of the catalyst since the step of H 2 O vapor purging caused the over-oxidation of the Cu. In the revised manuscript, we have modified our TPSR experiments. As shown in Figure R1, the inverse and normal catalysts were firstly treated under WGS conditions, and then purged with Ar, which ensured that the catalysts underwent the real status as the WGS reaction. Then CO was introduced afterwards to react with the active surface species. At this stage, the normal Cu/CeO 2 gave CO 2 : H 2 ratio of 2 : 1, which corresponded very well to the reaction of 2CO + 2−OH = 2 CO 2 + H 2 ， proving the pure associative mechanism. After Ar purging for the second time, H 2 O was introduced. No H 2 signal was detected by the MS, indicating that the H 2 O cannot be converted to H 2 and active oxygen atoms by the normal Cu/CeO 2 catalyst, further proving the associative mechanism. However, for the inverse CeO 2 /Cu catalyst, the CO 2 : H 2 ratio was 3 : 1, not 2 : 1, for the TPSR test. This meant that besides the surface hydroxyls, active oxygen atoms created by the dissociation of H 2 O were also involved in the reaction. Additionally, H 2 was generated after only H 2 O injection. These results definitely confirmed that redox mechanism was present for the inverse CeO 2 /Cu, together with the associative mechanism. Then, we in purpose used H 2 to remove the surface oxygen but preserved surface hydroxyl on the catalyst, and then CO was filled in again. At this stage, the inverse CeO 2 /Cu catalysts gave CO 2 : H 2 ratio of 2 : 1, showing the typical results of associative mechanism, which was due to the consumption of the reactive oxygen species by purged H 2 . The same experiment was repeated three times in a row, and the results were very repeatable. From the above experiments, we confidently concluded that both the redox and associative mechanism were present in the WGS reaction catalyzed by the inverse CeO 2 /Cu catalyst. Neither of which could be ruled out. These important results were added in the revised manuscript as Figure 4a and b and the relevant discussion was supplemented (please see page 10, line 1-11, page 11, line 1-9).

The dissociation of H 2 O to H 2 is directly related to defect sites in the catalyst. To
further study the role of defect sites, we designed and performed in-situ Raman experiments. The similar procedure with TPSR was applied by using cyclic CO and H 2 O treatment under 200 °C. As shown in Figure R2a, two characteristic peaks, namely F 2g peak of CeO 2 2 and surface defect (oxygen vacancy) peak of D (Guo, M. et al. Langmuir, 2011, 27, 3872), could be observed. It is surprising that when CO was introduced, the defect peak (D) of inverse CeO 2 /Cu was greatly pronounced, even exceeding the CeO 2 F 2g peak.
When H 2 O was introduced, the defect peak was clearly weakened. This meant that the introduction of CO induced the creation of surface vacancies through the reaction of CO + O → CO 2 and CO + −OH → CO 2 + 1/2H 2 . The normal Cu/CeO 2 went through the same experiment ( Figure R2b), showing apparently fewer defect sites. These results suggested that for inverse CeO 2 /Cu, the surface defect sites related to Ce 3+ were easily generated under WGS conditions. Also the strong ability of H 2 O association catalyzed by the surface defects of CeO 2 ensured the very high WGS activity. These important data were added in the revised manuscript as Figure 5 and relevant discussion was supplemented (please see page 12, line 3-7, page 13, line 1-10).
In-situ Raman experiments were also conducted under the WGS conditions. As shown in Figure R3a, the inverse CeO 2 /Cu also gave more pronounced signal of surface defects under the WGS conditions. However, the in-situ Raman results of pure CeO 2 gave a dominant CeO 2 F 2g peak with very strong intensity ( Figure R3b), which was quite different to that for the inverse CeO 2 /Cu catalyst. The quantified results showed that the inverse CeO 2 /Cu possessed abundant defect sites under WGS conditions, with D/F 2g larger than 1.6. These results also suggested that defect sites (Ce 3+ ) were very easily generated under the WGS reaction conditions. We have measured the H 2 O reaction orders of the catalysts (Supplementary In one word, for the inverse catalyst, the surface oxygen of CeO 2 could be easily removed by CO to form defects. H 2 O dissociated on the defects and H 2 was generated, confirming the redox mechanism. Meanwhile, CO also reacted with surface hydroxyl to form CO 2 and H 2 , following the associative mechanism. Therefore, both the redox mechanism and the associative mechanism were present in the WGS reaction catalyzed by the inverse CeO 2 /Cu catalyst. The described results were shown as Figure 4 and Figure 5 in the revised manuscript and relevant discussion was supplemented. The cartoon in Scheme 1 has also been modified.

Comment 1: In this contribution entitled "Construction of stabilized bulk-nano interfaces for
highly promoted inverse CeO 2 /Cu catalyst" by Yan and co-workers the authors describe the preparation of an inverse CeO 2 /Cu catalyst and its application in the water-gas shift reaction.
This reaction is of great importance for the future generation of hydrogen and its context in the field of energy harvesting. The topic is timely and the data presented in the paper is interesting and convincing and mostly provides evidence and answers to readers.
Author Reply: We sincerely thank for the reviewer's kind comment. Besides, using Cu as catalyst support is comparatively more economic than noble metal. In the revised manuscript, we have cited the articles recommended by the reviewer in the introduction (Reference 25-27). Thanks for the comment again.

Comment 3: On page 4 (end of introduction): it should read CO oxidation and not reduction
Author Reply: The reviewer's comment is highly appreciated. We are sorry for this careless mistake. The revised manuscript has been carefully examined and these errors were corrected. Author Reply: We thank for the reviewer's comment. According to the reviewer's concern, we have calculated the Cu surface areas from the dispersion, and the reaction rates in terms of Cu surface area and Cu loading, as shown in Table R1. As shown in Figure R4a, when the reaction rates were calculated with Cu loading, the normal Cu/CeO 2 gave higher r than inverse CeO 2 /Cu since it contained much less Cu content. In our manuscript, we found that the active site for the inverse catalyst lied in the Cu-CeO 2 interface, rather than metallic Cu. With this premise, the WGS reaction rate would not be accurate in terms of Cu loading. Moreover, the calculated S Cu for inverse CeO 2 /Cu and normal Cu/CeO 2 were larger than their S BET . Such phenomenon has been reported in previous literatures (For example, Cu-Zn-Al in Velu S. et al. Catal. Lett. 1999, 62, 159). We have mentioned in the manuscript that CeO 2 was found to participate in N 2 O chemisorption, causing higher Cu dispersion (Wang W. et al. ACS Catal. 2017, 7, 1313-1329. We calculated the Cu surface area of Cu-Zn-Al catalyst (19.7 m 2 g -1 ), which was much lower than that of inverse CeO 2 /Cu. Thus, though the reaction rate of inverse CeO 2 /Cu was higher than that of normal Cu/CeO 2 ( Figure R4b), the accuracy of the reaction rate derived from S Cu could not be ensured in this system. This was the reason we did not put these data in our manuscript. As for the reviewer's concern of quantified parameter, it was difficult because we cannot obtain useful information from TEM or STEM. However, we have made efforts to obtain and compare the TOF between the inverse and normal catalysts, and the results were convincing. First, we built a model for inverse CeO 2 /Cu catalysts ( Figure  Where r was the reaction rate, N av was Avogardro's constant, m CeO2 was the weight of the CeO 2 nanoparticle (assuming the semispherical shape, derived from its volume and density, 7.21 g cm -3 ), X CeO2 was the CeO 2 concentration of the catalyst, 16 was the site density of Ce atoms along the periphery, and d was the crystalline size of CeO 2 (3 nm). By using the above formula, the calculated TOF of inverse CeO 2 /Cu was 0.058 s -1 .
For the normal Cu/CeO 2 catalyst, we applied the formula below to obtain TOF of the single At the same time, we must note that the model for TOF calculations was simplified. The inverse catalyst exhibited more promising redox properties compared with the normal one, which has been shown from the in-situ Raman results ( Figure R3). Therefore, the difference in activity between the inverse and normal catalyst could also come from the distinct ability in activating the reactants. Author Reply: The reviewer's comment is highly appreciated. We have repeated the measurement of activation energy toward both catalysts for 3 times. The tested catalysts were separately prepared before each measurement. As shown in Figure R6, the Ea for the inverse CeO 2 /Cu was from 36.9 to 37.3 kJ/mol, while that for normal Cu/CeO 2 was from 40.6 to 40.9 kJ/mol. The repeated results suggested that the E a of inverse CeO 2 /Cu was ~4 kJ/mol lower than that of normal Cu/CeO 2 . We have replaced   Figure 4) the authors postulate, however, such defect sites.
(see also the above mentioned publications)  Figure R2a, two characteristic peaks, namely In-situ Raman experiments were also conducted under the WGS conditions. As shown in Figure R3a, the inverse CeO 2 /Cu also gave more pronounced signal of surface defects under the WGS conditions. However, the in-situ Raman results of pure CeO 2 gave a dominant CeO 2 F 2g peak with very strong intensity ( Figure R3b), which was quite different to that for the inverse CeO 2 /Cu catalyst. The quantified results showed that the inverse CeO 2 /Cu possessed abundant defect sites under WGS conditions, with D/F 2g larger than 1.6. These results also suggested that defect sites (Ce 3+ ) were very easily generated under the WGS reaction conditions. We have measured the H 2 O reaction orders of the catalysts (Supplementary

Composite of the catalysts.
Our former work (Yan H. et al. Appl. Catal. B, 2018, 226, 182) has shown that for bulk catalysts containing large amount of Cu, the adsorption and OH stretching of H 2 O were very weak.

Preparation method of the catalysts.
In former report (Wang X. et al. J. Phys. Chem. B, 2006, 110, 428), the authors prepared Cu-CeO 2 catalysts with impregnation and reversed micro-emulsion method, respectively. The impregnated catalyst showed H 2 O signal in the DRIFTS spectra, while the catalyst prepared by reversed micro-emulsion method did not. The reversed micro-emulsion method is applied to obtain bulk catalysts, which is similar to the AASA method used in our manuscript.
In our manuscript, using in-situ DRIFT, we focused more on the detection of the adsorbed CO. However, no adsorbed CO signal was detected, as shown in Figure R7, which might be due to the dark color of the catalyst powder. there seems to be a lack of sufficient error analysis in the manuscript.
Author Reply: The reviewer's comment is highly appreciated. Uncertainty analysis is crucial for the evaluation of catalytic performances. In fact, every catalyst shown in this work has been tested at least twice. Specially, we have prepared and tested the inverse CeO 2 /Cu catalysts for three times. The tested catalysts were separately prepared before each measurement. As shown in Figure R8, the WGS activity was nearly the same. Author Reply: We greatly thank for the reviewer's comment. As for the concern of quantified parameter, it was difficult because we cannot obtain useful information from TEM. Where r was the reaction rate, N av was Avogardro's constant, m CeO2 was the weight of the CeO 2 nanoparticle (assuming the semispherical shape, derived from its volume and density, 7.21 g cm -3 ), X CeO2 was the CeO 2 concentration of the catalyst, 16 was the site density of Ce atoms along the periphery, and d was the crystalline size of CeO 2 (3 nm). By using the above formula, the calculated TOF of inverse CeO 2 /Cu was 0.058 s -1 .

However, we have made efforts to obtain and
For the normal Cu/CeO 2 catalyst, we applied the formula below to obtain TOF of the single site on Cu-CeO 2 interface (J. Phys. Chem. C, 2010, 114, 21605): Where r was the reaction rate, N av was Avogardro's constant, m Cu was the weight of the Cu nanoparticle (assuming the semispherical shape, derived from its volume and density, 8.92 g cm -3 ), X Cu was the Cu concentration of the catalyst, 8 was the site density of Cu atoms along At the same time, we must note that the model for TOF calculations was simplified. The inverse catalyst exhibited more promising redox properties compared with the normal one, which has been shown from the in-situ Raman results ( Figure R3). Therefore, the difference in activity between the inverse and normal catalyst could also come from the distinct ability in activating the reactants. Author Reply: The reviewer's comment is highly appreciated. We have repeated the measurement of activation energy toward both catalysts for 3 times. The tested catalysts were separately prepared before each measurement. As shown in Figure R6, the Ea for the inverse We have also gathered the Ea data of Cu-CeO 2 WGS catalysts. As shown in   Figure S4), and the signal of CeO 2 interacting with Cu species could be overlapped by bulk CeO 2 .
Moreover, for the inverse CeO 2 /Cu, although the CeO 2 nanoparticles showed enhanced redox properties (evidenced by TPR and TPD), it could be easily oxidized in air, giving typical Ce 4+ signals in ex-situ measurement (Figure 2d). We have also tried ex-situ XANES to examine the chemical state of Ce in inverse CeO 2 /Cu. As shown in Figure R9, the result also gave nothing more than Ce 4+ signal.

Figure R9
| XANES data. XANES spectra of fresh and used inverse CeO 2 /Cu catalysts.

In order to check the chemical state of Ce under reaction conditions, we performed
in-situ Raman experiments. We applied a similar procedure with TPSR, using cyclic CO and H 2 O treatment under 200 °C. As shown in Figure R2a, two characteristic peaks, namely F 2g peak of CeO 2 2 and surface defect (oxygen vacancy) peak of D (Guo, M. et al. Langmuir, 2011, 27, 3872), could be observed. It is surprising that when CO was introduced, the defect peak (D) of inverse CeO 2 /Cu was greatly pronounced, even exceeding the CeO 2 F 2g peak.
When H 2 O was introduced, the defect peak was clearly weakened. This meant that the introduction of CO induced the creation of surface vacancies through the reaction of CO + O → CO 2 and CO + −OH → CO 2 + 1/2H 2 . The normal Cu/CeO 2 went through the same experiment ( Figure R2b), showing apparently fewer defect sites. These results suggested that for inverse CeO 2 /Cu, the surface defect sites related to Ce 3+ were easily generated under WGS conditions. Also the strong ability of H 2 O association catalyzed by the surface defects of CeO 2 ensured the very high WGS activity. These important data were added in the revised manuscript as Figure 5 and relevant discussion was supplemented (please see page 12, line 3-7, page 13, line 1-10).
In-situ Raman experiments were also conducted under the WGS conditions. As shown in Figure R3a, the inverse CeO 2 /Cu also gave more pronounced signal of surface defects under the WGS conditions. However, the in-situ Raman results of pure CeO 2 gave a dominant CeO 2 F 2g peak with very strong intensity ( Figure R3b), which was quite different to that for the inverse CeO 2 /Cu catalyst. The quantified results showed that the inverse CeO 2 /Cu possessed abundant defect sites under WGS conditions, with D/F 2g larger than 1.6. These results also suggested that defect sites (Ce 3+ ) were very easily generated under the WGS reaction conditions. We have measured the H 2 O reaction orders of the catalysts (Supplementary   Author Reply: We thank for the reviewer's comment. We have found that the inverse CeO 2 /Cu catalyst shows surprisingly high WGS activity, considering its high Cu content. According to the reviewer's concern, we calculated the Cu surface areas, and the reaction rates in terms of Cu surface area and Cu loading. As shown in Figure R4a, when the reaction rates were calculated with Cu loading, the normal Cu/CeO 2 gave higher r than inverse CeO 2 /Cu since it contained much less Cu. In our manuscript, we found that the active site for the inverse catalyst lied in the Cu-CeO 2 interface, rather than metallic Cu. With this premise, the WGS reaction rate would not be accurate in terms of Cu loading. Moreover, the calculated S Cu for inverse CeO 2 /Cu and normal Cu/CeO 2 were larger than their S BET . Such phenomenon has been reported in previous literatures (For example, Cu-Zn-Al in Velu S. et al. Catal. Lett. 1999, 62, 159). We have mentioned in the manuscript that CeO 2 was found to participate in N 2 O chemisorption, causing higher Cu dispersion (Wang W. et al. ACS Catal. 2017, 7, 1313-1329. We calculated the Cu surface area of Cu-Zn-Al catalyst (19.7 m 2 g -1 ), which was much lower than that of inverse CeO 2 /Cu. Thus, though the reaction rate of inverse CeO 2 /Cu was higher than that of normal Cu/CeO 2 ( Figure R4b), the accuracy of r derived from S Cu could not be ensured in this system. This is the reason we did not put these data in our manuscript. Author Reply: We greatly thank for the reviewer. The manuscript has been thoroughly checked and many writing errors are found and corrected. For example, "CO reduction" in abstract and introduction was corrected to "CO oxidation". The unit in experimental section was unified as cm 3 min -1 rather than mL min -1 .
The authors have significantly change the original manuscript in response to the original comments, adding new information/experiments, revising their assumptions and conclusions about the mechanism and clarifying overall all the suggested points. I now recommend publication.
Reviewer #3 (Remarks to the Author): The authors have done a thorough job responding to the reviews, and I find that the manuscript is significantly improved and worthy of publication. I have only one small final question / comment: in discussing Figure 4, the authors write that "After H2O injection, we removed the surface oxygen with H2 reduction and preserved the surface hydroxyls, after which CO was purged into the system to conduct the TPSR test again. " How did they determine that the surface oxygen was removed but that the hydroxyls coverage was preserved?

Responses to the reviewers' comments
To Reviewer #1:  Figure 4, the authors write that "After H2O injection, we removed the surface oxygen with H2 reduction and preserved the surface hydroxyls, after which CO was purged into the system to conduct the TPSR test again. " How did they determine that the surface oxygen was removed but that the hydroxyls coverage was preserved?
Author Reply: We sincerely thank for the reviewer's kind comment. In our manuscript, we have found that the surface oxygen of inverse CeO 2 /Cu is easy to be removed. The surface oxygen can react with either CO (in WGS conditions) or H 2 (in pretreatment). Meanwhile, CO can react with surface hydroxyls, following the reaction: 1/2H + CO OH + CO 2 2 → Such reaction can be observed from Fig. 4a and b. When CO was introduced, the intensity of H 2 signal was increased. The consumption of surface hydroxyls generates H 2 , so the reaction of H 2 with surface hydroxyls is not likely to occur. Thus, we use H 2 treatment to remove surface oxygen and preserve surface hydroxyls. We have also conducted such experiments in our former work (Fu X. et al. J. Am. Chem. Soc. 2019, 141, 4613).