Nickel Nanoparticles Decorated on Glucose-Derived Carbon Spheres as a Novel, Non-Palladium Catalyst for Epoxidation of Olefin
Round 1
Reviewer 1 Report
Manuscript of Alhumaimess describes the use Ni-nanoparticles for the epoxidation of some alkenes. Although alkene epoxidation is a well known and optimized reaction, the approach here proposed seems to be interesting, thus I suggest the publication after some revisions below reported:
· the meaning of CSs should be explained in the abstract
· the literature must be improved, introducing some important articles or review on this field (such as Nano Letters 2009, 9, 1501, Reviews in Chemical Engineering 2020, 36, 459, RSC Adv., 2019, 9, 27659, Chemosphere 2022, 297, 134172, Environmental Chemistry Letters 2022, 20, 1719, Molecules 2022, 27, 670, Coordination Chemistry Reviews 2022, 456, 214392
· line 52: in addition to the cited metals, also Mn should be cited and some examples of heterogenous Mn-catalysts must be reported
· manuscript contains many typos
· the mol/equivalents of reagents must be reported in the experimental procedure
· regarding the GC conditions, column, temperature of the oven must be detailed
· the amounts of reaction products (in %) must be reported in the text and in the Scheme 1
· in scheme 1, the hydrogen peroxide must be reported as reagent
· line 301: until now, the cyclohexene was the only substrate used
· in Figure 5b, the point relative to conversion value at pH 8 missing
· line 336: cyclooctene and cyclohexene are not aromatics
· mechanism reported in Figure 7 requires some experimental measurements. in absence of these, I suggest to remove this mechanism
· english must be strongly revised
Author Response
Dear Reviewer
We sincerely thank you and the reviewers for your constructive comments on our manuscript.
Manuscript ID: Catalysts-1955322
Title: "Nickel nanoparticles decorated on glucose-derived carbon spheres as a novel non-palladium catalyst for epoxidation of olefin”
Responding to the comments, we have carefully checked all valuable criticisms and suggestions from the referees and editor and have made suitable revisions. Please find our point-to-point answers to the referees and the revised version we made accordingly. For clear reasons, the revision parts were marked with red color, which we send as review-only materials. Thank you for your kind consideration of this paper.
Looking forward to hearing from you soon,
Sincerely yours,
Mosaed S. Alhumaimess
Response to Reviewer #1
Remark (1): The meaning of CSs should be explained in the abstract.
Response: The meaning of CSs abbreviation was explained in the abstract
Remark (2): The literature must be improved, introducing some important articles or reviews on this field (such as Nano Letters 2009, 9, 1501, Reviews in Chemical Engineering 2020, 36, 459, RSC Adv., 2019, 9, 27659, Chemosphere 2022, 297, 134172, Environmental Chemistry Letters 2022, 20, 1719, Molecules 2022, 27, 670, Coordination Chemistry Reviews 2022, 456, 214392.
Response: The corresponding references are cited in the revised version and took number [2-8] in the revised version.
Remark (3): line 52: in addition to the cited metals, also Mn should be cited and some examples of heterogenous Mn-catalysts must be reported.
Response: The corresponding references related to Mn catalysts are cited in the revised version and took number [19, 20] in the revised version.
Remark (4): manuscript contains many typos
- The mol/equivalents of reagents must be reported in the experimental procedure.
Response: The mol/equivalents of reagents were reported
- Regarding the GC conditions, the column, and temperature of the oven must be detailed.
Response: The detailed of GC was mentioned in the revised version
- The amounts of reaction products (in %) must be reported in the text and in Scheme 1.
Response: The sentences and Scheme 1 were corrected in the revised version (Page 7).
In scheme 1, the hydrogen peroxide must be reported as a reagent.
Response: The hydrogen peroxide was reported as a reagent in scheme 1
- Line 301: until now, cyclohexene was the only substrate used.
Response: Thank you and the referees for this constructive comment. We apologize for this mistake. The sentence was corrected as “The conversion and selectivity of a wider spectrum of alkenes at 353 K, pH 8, and using acetonitrile were illustrated in Table 2.
- In Figure 5b, the point relative to the conversion value at pH 8 missing.
Response: Figure 5b is re-drawn and the point relative to the conversion value at pH 8 is appeared.
- Line 336: cyclooctene and cyclohexene are not aromatics.
Response: The sentence was corrected
- The mechanism reported in Figure 7 requires some experimental measurements in absence of these, I suggest removing this mechanism.
Response: The mechanism was removed according to your suggestion.
- English must be strongly revised.
Response: Thank you and the referees for pointing this out. I have checked the manuscript carefully. One of my colleges, whose native language is English, has helped us to check it thoroughly, besides using Grammarly software.
Reviewer 2 Report
The author presented
Nickel nanoparticles decorated on glucose–derived carbon spheres as a novel non-palladium 2 catalyst for epoxidation of olefin
The work good for publication but marred with typo errors all through the manuscript
Major revision is needed
Introduction section
Line 11
in the reaction media and degradation of the catalytic performance due to nanoparticles NPs (the abbreviation should be used all through)
Paragraph 3 line 24
of catalysts for olefin epoxidation. Nasseri et al. [14] used silica to immobilize Fe3O4 NPs, ( 3 and 4 should be subscript)
Paragraph 3 line 26
moderate conditions. Ghiami et al. [15] employed FeNi3 3 should be subscript) NPs grafted silica in alkenes
Paragraph 3 line 30
Although the high activity of NiO allowed Abboud [19] to use of NiO NPs in the
Add these current articles to the introduction
1. Journal of Photochemistry and Photobiology B: Biology Volume 199, October 2019, 111601 https://doi.org/10.1016/j.jphotobiol.2019.111601
2. European Polymer Journal 2020, 122:109371. https://doi.org/10.1016/j.eurpolymj.2019.109371
3. J Nanobiotechnol 18, 172 (2020). https://doi.org/10.1186/s12951-020-00704-4
Section 2.1
Glucose (D(+), ≥99.5) used to prepare CSs, potassium carbonate (K2CO3, ≥ 99.9%), 82 Nickel(III) nitrate hexahydrate (Ni(NO3)26H2O, ≥ 99.9%), H2O2 (30 % in H2O), polyvi- 83 nyl alcohol (PVA) (Mw = 10000, 80%), cyclohexene (≥99.0%), NaHCO3 (≥99%), cyclohex- 84 ene (96%), 1-hexene (91%), cyclooctene (≥99) and styrene (≥99) were procured from 85 Sigma-Aldrich Co., USA. Hydrazine hydrate (80% solution in water) was obtained from 86 Merck, Germany. All materials were used with no further treatment. Distilled water pro- 87 vided in all measurements was obtained by Milli-Q direct 8 purification system (Milli- 88 pore, France). (All your chemical equations are wrong, kindly correct them using subscript)
Section 2.2, line 6 and 7
followed by ethanol before being dried at 80oC overnight. The CSs have been calcined for 5 hours at 700oC with a heating rate of 5o/min in a tube furnace under a nitrogen atmosphere. (kindly write your degree very well, use superscript all through)
section 2.3, line 3
dispersion was produced. After that, a certain amount of Ni (NO3)26H2O (Write this chemical equation very well )
section 2.4, line 3
eter. Shimadzu IR Tracer-100 was used to capture FTIR spectra in the 400-4000 cm-1 cm-1
line 6
alpha radiation -10 to 1350 eV, spot size 400 micro at pressure 10-9 (I presume the 10-9) mbar
line 9
Quantachrome GmbH & Co. KG, Boynton Beach, USA) was used to obtain the N2 (N2) iso-
Section 2.5
(2 ml). H2O2 (30%, 2 mL), and NaHCO3 (2 mmol, 0.17 g). (correct the chemical equations)
Section 3.1
FT-IR spectra of the prepared CSs and Ni@CSs composites are illustrated in Figure 141 1a. The spectrum of the as synthesized CSs calcined at 700oC displaying the following 142 absorption bands: a wide absorption peak from 3000 to 3500 cm-1 due to O-H stretching, 143 a weak peak at 2900 cm−1 assigned to aliphatic C-H stretching modes, characteristics 144 bands at 1614 and 1717 cm−1 are attributed to C=C, and C=O modes respectively, and 145 bands between 500 and 900 cm-1 are mainly related to C-H bending modes. The FTIR 146 spectra of (5 & 10%) Ni@CSs composites are virtually identical. However, the absorption 147 bands grow reduced after the loading of Ni nanoparticles, implying that the CSs surface 148 functionality remained intact (kindly write well using superscript)
Section 3.1, line 11
sites containing different Ni content. The wide diffraction peaks at 2θ = 21.8°, 25.8o 25.8o, and 26.3o 26.3o
Section 3.1, paragraph 3 line 1-3
Figure 1c. Two distinct bands in the Raman spectrum of CSs , the D peak at 1343 cm- 1 cm- 1 and the G peak at 1585 cm- 1 cm- 1 , are ascribed to sp3 and sp2-carbon, respectively, [21]. The 158 Raman spectrum of Ni@CSs composite showed the identical band at 1348 and 1598 cm- 1 cm- 1
Below table 1
aThe values between the brackets is represent the atomic % of the element
The first paragraph under table 1, line 5
288.6 eV, which is related to the C=C, C–O,
Section 3.3.2
Initially, an effervescence is observed in the absence of the catalyst when a mixture 270 of H2O2 and NaHCO3 is added to cyclohexene and acetonitrile mixture, and by analyzing 271 the arising gas is identified as oxygen, which describes the epoxidation process’ declines. 272 In Figure 5b, the ratio of H2O2 to mol of NaHCO3 was varied to achieve pH values rang- 273 ing from 5 to 10. After 14 hours at pH 8, the impact of pH value on the epoxidation per- 274 formance at 353 K is determined. In the epoxidation process catalyzed by 10% Ni@CSs to 275 activate hydrogen peroxide, the introducing of NaHCO3 was completely significant, with 276 roughly 1.3% cyclohexene conversion produced after 2 hours in the absence of NaHCO3. 277 The cyclohexene conversion increased from 30% to 72% when the reaction pH was raised 278 from 5 to 7. Furthermore, at pH 8, there was a significant rise in cyclohexene conversion 279 of up to 90%. At a pH of 8, the volcano-curve with pH can be associated with the produc- 280 tion of adequate amounts of HCO4– species. Because peroxymonocarbonate (HCO4) is 281 the most powerful in boosting the process, the H2O2 and NaHCO3 mixture displays high 282 efficiency towards the synthesis of epoxide, according to Yao and Richardson [23]. Once 283 the NaHCO3 concentration rises to a pH of 10, however, epoxidation dropped to about 284 58 %. (all your chemical equations in this section are wrong, kindly correct them)
Section 3.3.5, line 8
The cyclohexene conversion of was of 98% (cyclohexene).. (what is the meaning of this statement?)
Author Response
Dear Reviewer
We sincerely thank you and the reviewers for your constructive comments on our manuscript.
Manuscript ID: Catalysts-1955322
Title: "Nickel nanoparticles decorated on glucose-derived carbon spheres as a novel non-palladium catalyst for epoxidation of olefin”
Responding to the comments, we have carefully checked all valuable criticisms and suggestions from the referees and editor and have made suitable revisions. Please find our point-to-point answers to the referees and the revised version we made accordingly. For clear reasons, the revision parts were marked with red color, which we send as review-only materials. Thank you for your kind consideration of this paper.
Looking forward to hearing from you soon,
Sincerely yours,
Mosaed S. Alhumaimess
Response to Reviewer #2
Introduction section
Remark (1): Line 11: in the reaction media and degradation of the catalytic performance due to nanoparticles NPs (the abbreviation should be used all through)
Response: The abbreviation was used through all the revised manuscript.
Remark (2): Paragraph 3 line 24: of catalysts for olefin epoxidation. Nasseri et al. [14] used silica to immobilize Fe3O4 NPs, (3 and 4 should be subscript).
Response: The symbol was corrected in the revised version.
Remark (3): Paragraph 3 line 26: moderate conditions. Ghiami et al. [15] employed FeNi3 3 should be subscript) NPs grafted silica in alkenes.
Response: The symbol was corrected in the revised version.
Remark (4): Paragraph 3 line 30: Although the high activity of NiO allowed Abboud [19] to use of NiO NPs. Add these current articles to the introduction
- 1. Journal of Photochemistry and Photobiology B: Biology Volume 199, October 2019, 111601 https://doi.org/10.1016/j.jphotobiol.2019.111601
- European Polymer Journal 2020, 122:109371.https://doi.org/10.1016/j.eurpolymj.2019.109371
- 3. Nanobiotechnol 18, 172 (2020).https://doi.org/10.1186/s12951-020-00704-4
Response: The corresponding references are cited in the revised version and took number [1-3] in the revised version.
Section 2.1
Remark (5): Glucose (D(+), ≥99.5) used to prepare CSs, potassium carbonate (K2CO3, ≥ 99.9%), 82 Nickel(III) nitrate hexahydrate (Ni(NO3)26H2O, ≥ 99.9%), H2O2 (30 % in H2O), polyvi- 83 nyl alcohol (PVA) (Mw = 10000, 80%), cyclohexene (≥99.0%), NaHCO3 (≥99%), cyclohex- 84 ene (96%), 1-hexene (91%), cyclooctene (≥99) and styrene (≥99) were procured from 85 Sigma-Aldrich Co., USA. Hydrazine hydrate (80% solution in water) was obtained from 86 Merck, Germany. All materials were used with no further treatment. Distilled water pro- 87 vided in all measurements was obtained by Milli-Q direct 8 purification system (Milli- 88 pore, France). (All your chemical equations are wrong, kindly correct them using subscript)
Response: Section 2.1 was corrected.
Remark (6): Section 2.2, line 6 and 7: followed by ethanol before being dried at 80oC overnight. The CSs have been calcined for 5 hours at 700oC with a heating rate of 5o/min in a tube furnace under a nitrogen atmosphere. (Kindly write your degree very well, use superscript all through)
Response: Section 2.2 was corrected.
Remark (7): Section 2.3, line 3: dispersion was produced. After that, a certain amount of Ni (NO3)26H2O (Write this chemical equation very well).
Response: The chemical formula of nickel nitrate was corrected as Ni(NO3)2 . 6H2O.
Remark (8): Section 2.4, line 3:eter. Shimadzu IR Tracer-100 was used to capture FTIR spectra in the 400-4000 cm-1 cm-1
Response: The sentence was corrected in the revised version.
Remark (9): line 6: alpha radiation -10 to 1350 eV, spot size 400 micro at pressure 10-9 (I presume the 10-9) mbar
Response: The pressure was corrected to 10-9 mbar
Remark (10): line 9: Quantachrome GmbH & Co. KG, Boynton Beach, USA) was used to obtain the N2 (N2) iso-
Response: The sentence was corrected in the revised version.
Remark (11): Section 2.5: (2 ml). H2O2 (30%, 2 mL), and NaHCO3 (2 mmol, 0.17 g). (correct the chemical equations)
Response: All chemical formula were corrected in the revised version.
Remark (12): Section 3.1: FT-IR spectra of the prepared CSs and Ni@CSs composites are illustrated in Figure 141 1a. The spectrum of the as synthesized CSs calcined at 700oC displaying the following 142 absorption bands: a wide absorption peak from 3000 to 3500 cm-1 due to O-H stretching, 143 a weak peak at 2900 cm−1 assigned to aliphatic C-H stretching modes, characteristics 144 bands at 1614 and 1717 cm−1 are attributed to C=C, and C=O modes respectively, and 145 bands between 500 and 900 cm-1 are mainly related to C-H bending modes. The FTIR 146 spectra of (5 & 10%) Ni@CSs composites are virtually identical. However, the absorption 147 bands grow reduced after the loading of Ni nanoparticles, implying that the CSs surface 148 functionality remained intact (kindly write well using superscript).
Response: Section 3.1 was corrected.
Remark (13): Section 3.1, line 11: sites containing different Ni content. The wide diffraction peaks at 2θ = 21.8°, 25.8o 25.8o, and 26.3o 26.3o
Response: Section 3.1, Line 11 was corrected.
Remark (14): Section 3.1, paragraph 3 line 1-3: Figure 1c. Two distinct bands in the Raman spectrum of CSs , the D peak at 1343 cm- 1 cm- 1 and the G peak at 1585 cm- 1cm- 1 , are ascribed to sp3 and sp2-carbon, respectively, [21]. The 158 Raman spectrum of Ni@CSs composite showed the identical band at 1348 and 1598 cm- 1 cm- 1
Response: Section 3.1, paragraph 3 Line 1-3 was corrected.
Remark (15): Below table 1: aThe values between the brackets is represent the atomic % of the element The first paragraph under table 1, line 5 288.6 eV, which is related to the C=C, C–O,
Response: All the sentences were corrected
Remark (16): Section 3.3.2: Initially, an effervescence is observed in the absence of the catalyst when a mixture 270 of H2O2 and NaHCO3 is added to cyclohexene and acetonitrile mixture, and by analyzing 271 the arising gas is identified as oxygen, which describes the epoxidation process’ declines. 272 In Figure 5b, the ratio of H2O2 to mol of NaHCO3 was varied to achieve pH values rang- 273 ing from 5 to 10. After 14 hours at pH 8, the impact of pH value on the epoxidation per- 274 formance at 353 K is determined. In the epoxidation process catalyzed by 10% Ni@CSs to 275 activate hydrogen peroxide, the introducing of NaHCO3 was completely significant, with 276 roughly 1.3% cyclohexene conversion produced after 2 hours in the absence of NaHCO3. 277 The cyclohexene conversion increased from 30% to 72% when the reaction pH was raised 278 from 5 to 7. Furthermore, at pH 8, there was a significant rise in cyclohexene conversion 279 of up to 90%. At a pH of 8, the volcano-curve with pH can be associated with the produc- 280 tion of adequate amounts of HCO4– species. Because peroxymonocarbonate (HCO4) is 281 the most powerful in boosting the process, the H2O2 and NaHCO3 mixture displays high 282 efficiency towards the synthesis of epoxide, according to Yao and Richardson [23]. Once 283 the NaHCO3 concentration rises to a pH of 10, however, epoxidation dropped to about 284 58 %. (all your chemical equations in this section are wrong, kindly correct them).
Response: All the chemical formula were corrected in the revised version.
Remark (17): Section 3.3.5, line 8: The cyclohexene conversion of was of 98% (cyclohexene).. (what is the meaning of this statement?)
Response: The sentence was revised and corrected.
Round 2
Reviewer 2 Report
Accept for publication
