Pt Nanowire-Anchored Dodecahedral Ag3PO4{110} Constructed for Significant Enhancement of Photocatalytic Activity and Anti-Photocorrosion Properties: Spatial Separation of Charge Carriers and PhotogeneratedElectron Utilization
Round 1
Reviewer 1 Report
Comment:
In present manuscript author reported, ‘Pt nanowires-anchored dodecahedral Ag3PO4{110} constructed for significant enhancement of photocatalytic activity and anti-photocorrosion: spatial separation of charge carriers and photogenerated electron utilization’ The interesting thing is dodecahedral Ag3PO4 achieved higher photocatalytic activity than other Silver salts crystals. Also, 1D Pt nanowires loaded on dodecahedral Ag3PO4 shows improved the charge carrier’s separation due to the formation of Schottky barrier. The SEM images, spectrums and experimental section all are sufficient for explanation, but references are not in correct format, need to write tetrahedron letters format. This manuscript is overall well written, presented in a scholarly manner, enough references and publishable without further correction.
Author Response
Reply as: Already revised. According to the comment, we have revised the references in correct format.
References
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Reviewer 2 Report
Manuscript catalysts-690901 describes Pt nanowires-anchored dodecahedral Ag3PO4{110} constructed for significant enhancement of photocatalytic activity and anti-photocorrosion: spatial separation of charge carriers and photogenerated electron utilization. The work is interesting, however some additional results and comments would be included before publication. In general, the prepared catalysts were widely characterized, but in terms of catalytic activity more detailed information would be added.
The new achievements carried out with this work would be emphasized. The novelty of the work was not reported. In general, the prepared catalysts were widely characterized, but in terms of catalytic activity more detailed information would be added. The photocatalytic activity was only evaluated under the same experimental conditions. The effect of other pollutant and catalyst concentrations, irradiation source, among other parameters, was not reported. The influence of these conditions would be considered before publication. The catalytic activity was only evaluated by the absorption at 554 nm measured with a UV–vis spectrophotometer. This measurement allows evaluate the degradation of RhB, however, no consideration about the organic matter was taken into account. In terms of catalytic activity, the formation of intermediates is very important and the efficiency of the process strongly depends on it. Evaluate the formation of by-products by other techniques (for example HPLC), and/or determine the amount of organic matter presented in solution is very important. In Figure 4, the profile of photolysis would be added, in order to verify the difference between non-catalytic and catalytic runs. The colored background of Figure 5 would be removed, in order to facilitate the interpretation of the results. In the same Figure the results would be separated by catalyst and not by runs (example in Figure 5 a) would present the results of catalytic activity of irregular spherical Ag3PO4 sample for all cycles. The performances of tested catalysts would be compared with the literature. In spite of the properties of catalysts were detailed study, a comparison with reported results would be considered in order to understand the novelty of the work.
Author Response
Reply as: Already revised. According to your suggestions, the influences of reaction conditions (pollutant and catalyst concentrations, irradiation source) on photocatalytic activity were investigated.
Revised Section - 3.3 Photocatalytic activity and anti-photocorrosion
Due to absolute exposure of {110} facet, the Ag3PO4 rhombic dodecahedrons showed higher photocatalytic activity than Ag3PO4 irregular spheres. In addition, compared with loading of particles Pt, loading of 1D Pt nanowires on Ag3PO4 rhombic dodecahedrons can separate and transfer photo-induced electrons more efficiently, resulting in generation of more holes for RhB degradation. Thus, Pt nanowires-anchored dodecahedral Ag3PO4 achieved much higher photocatalytic activity than Pt-particles/dodecahedral Ag3PO4. The concentration of pollutants was no changed during the photolysis test, while more than 98% of RhB is photodegraded over Pt nanowires-anchored dodecahedral Ag3PO4 within 12 min (Fig. 3A). All the degradation kinetics of RhB in this experiment can be well described by the pseudo-first-order kinetic model (Fig. 3B). The rate constant of Pt nanowires-anchored dodecahedral Ag3PO4 (0.334 min-1) is 1.67 times higher than that of irregular spherical Ag3PO4 (0.125 min-1). In addition, the content of Pt nanowires showed obvious influence on photocatalytic activity. In the experiment range (0.2 ωt%, 0.5 ωt%, 1 ωt%, 2 ωt%), 0.5 ωt% Pt nanowires-anchored dodecahedral Ag3PO4{110} exhibited the highest degradation rate of RhB (Fig. 3C, D). UV–vis absorption spectra (inset of Fig. 3D) of RhB showed that RhB is completely degraded over 0.5 ωt% Pt nanowires-anchored dodecahedral Ag3PO4 within 10 min. Moreover，bisphenol A (BPA) and its intermediates could also be photodegraded efficiently over 0.5 ωt% Pt nanowires-anchored dodecahedral Ag3PO4{110}, resulting in 80% removal rate of TOC (Fig. S6). Further studies indicated that increase of light intensity, catalyst dosage and pollutant concentration could improve the degradation kinetics (Table. S1). However, excess loading of Pt nanowires on dodecahedral Ag3PO4 can cover the active facet (Fig. S3), resulting in the decrease of photocatalytic activity.
Moreover over, we add the various catalysts activity (reported in previous literatures) as comparison in Table S1, which indicates that the novel photocatalyst exhibits excellent photocatalytic activity.
Table. S1. Photocatalytic degradation of RhB over Ag3PO4-based photocatalysts in previous literatures
|
Photocatalyst |
Light source |
Pollutant concentration |
Degradation |
Reference |
|
Ag3PO4 porous microcubes (0.375g/L) |
500W Xe lamp (λ ≥ 400 nm) |
8ppm |
95% RhB degraded within 24 min |
1 |
|
Branch Ag3PO4 crystal (0.83g/L) |
350W (λ ≥ 400 nm) |
10ppm |
98% RhB degraded within 35 min |
2 |
|
Ag3PO4 tetrapods (1g/L) |
300W (λ ≥ 400 nm) |
8ppm |
95% RhB degraded within 15min |
3 |
|
Ag/Ag3PO4 coaxial hetero-nanowires (2g/L) |
300W (λ ≥ 400 nm) |
8ppm |
98% RhB degraded within 6min |
4 |
|
Pd(0.1wt%)/Ag3PO4 (1g/L) |
300W (λ ≥ 400 nm) |
5ppm |
95% RhB degraded within 15min |
5 |
|
Au(0.1wt%)/Ag3PO4 (1g/L) |
300W (λ ≥ 400 nm) |
5ppm |
94% RhB degraded within15min |
|
|
0.5ωt% Pt nanowires-anchored dodecahedral Ag3PO4 (0.3g/L) |
350W (λ ≥ 400 nm) |
5ppm |
99.5% RhB degraded within 10 min |
|
|
0.5ωt% Pt nanowires-anchored dodecahedral Ag3PO4 (0.3g/L) |
500W (λ ≥ 400 nm) |
5ppm |
98% RhB degraded within 5min |
|
|
0.5ωt% Pt nanowires-anchored dodecahedral Ag3PO4 (0.3g/L) |
350W (λ ≥ 400 nm) |
10ppm |
99% RhB degraded within 10min |
|
|
0.5ωt% Pt nanowires-anchored dodecahedral Ag3PO4 (1g/L) |
350W (λ ≥ 400 nm) |
5ppm |
98% RhB degraded within 3min |
|
Supplementary References
[1] Q. Liang, W. Ma, Y. Shi, Z. Li, X. Yang, CrystEngComm 14 (2012).
[2] P. Dong, Y. Wang, H. Li, H. Li, X. Ma, L. Han, J. Mater. Chem. A 1 (2013) 4651.
[3] J. Wang, F. Teng, M. Chen, J. Xu, Y. Song, X. Zhou, CrystEngComm 15 (2013) 39-42.
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Author Response File: 
Author Response.pdf
Reviewer 3 Report
Manuscript Title:
Pt nanowires-anchored dodecahedral Ag3PO4{110} constructed for significant enhancement of photocatalytic activity and anti-photocorrosion: spatial separation of charge carriers and photogenerated electron utilization
This manuscript studies the effect of Pt nanowires-anchored dodecahedral Ag3PO4{110} for photocatalytic degradation of organic dyes like RhB.
The prepared sample was deeply characterized through different technique. X-ray diffraction indicates that all the diffraction peaks of samples are indexed to the body-centered cubic phase Ag3PO4 and the presence of Pt nanowires-anchored dodecahedral well maintained the origin crystal structure of Ag3PO4.
The results obtained showed that the bandgap of dodecahedral Ag3PO4{110} (2.35 eV) is lower than that of Ag3PO4 irregular spheres (2.42 eV). Moreover, from the photocurrent measurement Pt nanowires-anchored dodecahedral Ag3PO4{110} achieved much higher photocurrent response than Pt particles/dodecahedral Ag3PO4{110}. As reported by the authors, such improvement of photocurrent response and electronic conductivity confirmed the enhancement of charge carriers separation and transfer of Pt nanowires-anchored dodecahedral Ag3PO4.
The best catalytic activity was obtained with 0.5 ωt% Pt nanowires-anchored dodecahedral Ag3PO4 within 10 min showed that RhB is completely degraded.
In addition, the authors reported that the presence of Pt on Ag3PO4 also showed excellent stability in long-time activity test.
The topic is interesting but there are some aspects that the authors should improve. The manuscript could be published after minor revision.
Abstract:
Please add some characterization results.Materials and method:
Please specify if during the phtocatalytic tests the temperature was monitored, and in which way?Results and discussion:
Add the photolysis test. Please clarify this important aspect. Increase the quality of Figure 5AAuthor Response
(1) Abstract: Please add some characterization results.
Reply as: Already revised. According to the suggestions, we added the characterization results (SEM, TEM and XRD) in the abstract.
(2) Materials and method: Please specify if during the phtocatalytic tests the temperature was monitored, and in which way?
Reply as: Already revised. The temperature of the reactor was monitored by a thermometer and maintained at 25 ± 2℃ by waterbath circulating system.
(3)Results and discussion: Add the photolysis test. Please clarify this important aspect. Increase the quality of Figure 5A
Reply as: Already revised. We have corrected Fig. 4 and Fig. 5A according to your suggestion. The photolysis tests were added in revised manuscript, and the quality of Figure 5A was improved in the revised manuscript.
Author Response File: Author Response.pdf
Reviewer 4 Report
In this manuscript, Zhu et al. reported the preparation and photocatalytic activity of Pt nanowires-anchored dodecahedral Ag3PO4{110}. There is one critical issue to be addressed before acceptance.
The Authors have been tested visible light-activity of prepared photocatalysts by using RhB dye as a model compound. The application of organic dyes as model compounds to test visible light photocatalysts is rather not good selection. Please consider the papers: Rochkind et al., Molecules 2015, 20, 88, doi:10.3390/molecules20010088 and Yan X. et al., Chem. Phys. Lett. 2006, 429, 606.
Author Response
Reply as: Already revised. Thank you for your suggestions. Besides RhB, we also tested the photocatalytic degradation of BPA, which exhibited the excellent visible light-activity of prepared photocatalysts. The concentration of bisphenol A and the intermediate products during the degradation process were analyzed by HPLC. In addition, TOC removal was also tested, which can directly evaluate the mineralization of organics during the photocatalytic degradation process. As shown in Fig. S6, both HPLC and TOC results indicated that organics could be well removed over catalysts.
Section 3.3 Photocatalytic activity and anti-photocorrosion
In order to comprehensive evaluate the visible-light photocatalytic activity of samples [43], photocatalytic degradation tests of bisphenol A (BPA) was also conducted. As a result, BPA and its intermediates could also be photodegraded efficiently over 0.5 ωt% Pt nanowires-anchored dodecahedral Ag3PO4{110}, resulting in 80% removal rate of TOC (Fig. S6). Further studies indicated that increase of light intensity, catalyst dosage and pollutant concentration could improve the degradation kinetics (Table. S1).
In addition, in our previous studies and other literatures, dyes and some phenolic compounds could be used to evaluate the visible-light photocatalytic activity (Applied Catalysis B: Environmental, 250 (2019) 31-41; 232(2018) 574-586; 203 (2017) 964–978). We add the papers (Yan X. et al., Chem. Phys. Lett. 2006, 429, 606) in our references.
[43] X. Yan, T. Ohno, K. Nishijima, R. Abe, Bunsho Ohtani Chem. Phys. Lett. 429 (2006) 606-610.
Author Response File: Author Response.pdf
Round 2
Reviewer 2 Report
The authors have taken into account the reviewers' considerations. Therefore, the paper can be published in the present form.
