Synthesis and Characterization of Pure ZnO and ZnO Supported MgF2 for Catalytic Acylation of Phenol

Synthesis and Characterization of Pure ZnO and ZnO Supported MgF2 for Catalytic Acylation of Phenol | Research Square window.SnipcartSettings = { analytics: { enabled: false } }; (function() { var accessVector = localStorage.getItem('access_vector') || ''; window.dataLayer = window.dataLayer || []; if (accessVector) { window.dataLayer.push({ user: { profile: { profileInfo: { snid: accessVector } } } }); } })(); (function(w,d,s,l,i){w[l]=w[l]||[];w[l].push({'gtm.start':new Date().getTime(),event:'gtm.js'});var f=d.getElementsByTagName(s)[0],j=d.createElement(s),dl=l!='dataLayer'?'&l='+l:'';j.async=true;j.src='https://www.googletagmanager.com/gtm.js?id='+i+dl;f.parentNode.insertBefore(j,f);})(window,document,'script','dataLayer','GTM-K279D39R'); Browse Preprints In Review Journals COVID-19 Preprints AJE Video Bytes Research Tools Research Promotion AJE Professional Editing AJE Rubriq About Preprint Platform In Review Editorial Policies Our Team Advisory Board Help Center Sign In Submit a Preprint Cite Share Download PDF Research Article Synthesis and Characterization of Pure ZnO and ZnO Supported MgF 2 for Catalytic Acylation of Phenol Ika Fitri Ulfindrayani, Irmina Kris Murwani, Eko Sri Kunarti, and 5 more This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-7593364/v1 This work is licensed under a CC BY 4.0 License Status: Published Journal Publication published 16 Feb, 2026 Read the published version in Transition Metal Chemistry → Version 1 posted 10 You are reading this latest preprint version Abstract The catalysts MgF 2 supported ZnO (0; 2.5; 5; 7.5; 10 and 15% w / w ) were synthesized by sol-gel method. The structure of the catalysts were characterized by XRD. The acidity of the catalyst determined by pyridine-FTIR method showed that 7.5% ZnO/MgF 2 had the highest acidity. The surface area of the ZnO/MgF 2 was measured by N 2 adsorption-desorption method. The surface area of the ZnO/MgF2 catalysts decrease with the increase in Zn content. The measurement SBET of the catalysts was in range of 5,31 to 9,44 m 2 /g. The morphology of the catalyst was observed by Scanning Electron Microscope (SEM). The synthesized catalysts performance was tested in phenol acylation and were determined by High Performance Liquid Chromatography (HPLC), which the main products were p -HAP (hydroxyacetophenone) and PA (phenyl acetate). The formation of p -HAP was influenced by the Lewis acid site, while PA was influenced by the Brønsted acid site. The highest conversion was achieved 85.36% by 7.5% ZnO/MgF 2 , while the yields of the p -HAP and PA were 56.06 and 23.40% respectively. acylation of phenol cactalyst ZnO/MgF2 hydroxyacetophenone Figures Figure 1 Figure 2 Figure 3 Figure 4 Figure 5 Figure 6 Figure 7 Figure 8 Figure 9 1. Introduction Phenol and its derivatives have been massively used in pharmaceutical field.[ 1 ] For instance, o-HAP (orto-hydroxyacetophenone) and p-HAP (orto-hydroxyacetophenone) are examples of phenol’s derivatives widely used as precursor to produce aspirin and paracetamol. o -HAP is intermediates in producing of 4-hydroxicoumarin and warfarin which are used as anticoagulant drugs in the therapy of thrombotic diseases.[ 2 ] Meanwhile, p -HAP is used in a process to obtain paracetamol.[ 3 ] HAP can be synthesis through phenol acylation via Fries rearrangement. Fries rearrangement is carried out in the presence of acid catalysts[ 4 ] such as ZnCl 2 [ 5 ], [ 6 ] to improve the yield of HAP.[ 7 ] However, this synthesis approach is far from an environmental friendly due to its toxicity and corrosive properties. In addition this method requires a large amount of catalyst and difficult separation process between catalysts and products.[ 8 ], [ 9 ] For these reasons, the synthesis of HAP has shifted by using solid catalyst because it is easy to separate the final product and catalyst.[ 10 ], [ 11 ] Metal oxide has been widely used in the synthesis of HAP due to its has high acidity, rapid reaction, easy reaction conditions and environmental friendly.[ 2 ], [ 3 ], [ 12 ] Tamaddon et al.[ 12 ] reported that the most efficient metal oxide for synthesis of hydroxyacetophenone is zinc oxide (ZnO). Many research has proven that ZnO has good ability as a catalyst or catalyst support.[ 13 ]–[ 20 ]. In 2005, Sarvari, M. H. and Sharghi, H. conducted phenol acylation reaction with ZnO catalyst at room temperature and solvent free conditions which achieved a yield of 94%.[ 21 ] The use of ZnO in other phenol acylation reactions was also carried out by Moghaddam, F. M. and Saeidian, H. (2007).[ 22 ] In their research, Moghaddam, F. M. and Saeidian, H. reacted phenol with acetyl chloride at room temperature for 5 minutes and the yield obtained was 95%. However, the reaction that occurs in some studies with ZnO catalysts is an O acylation reaction. In the acylation of phenol, there are two kinds of acylation that may occur, namely C acylation and O acylation. In the C acylation process, acylation on phenol directly produces HAP compounds while in O acylation, HAP compounds are not directly formed but through phenyl acetate intermediates which can later produce HAP compounds through Fries rearrangement. According to Padró and Apesteguía (2004), this Fries rearrangement requires an acidic catalyst so that the formation of HAP compounds through phenol acylation reactions can take place with the help of acidic catalysts. In the phenol acylation reaction, the acidity of a catalyst affects the products produced.[ 7 ], [ 23 ] Therefore, in this study it is necessary to increase the acidity of the ZnO catalyst. According to Wojciechowska et al.[ 24 ], the increasing of catalyst acidity can be achieved by providing catalyst support because it can affect the active site of the catalyst during the catalysis process. MgF 2 has conditions as a catalyst support such as high thermal stability (500°C), inert surface, high hardness and large surface area. Besides that, the addition of catalyst support can increase the surface area of the catalyst. In this research, ZnO supported MgF 2 (ZnO/MgF 2 ) catalyst will be used to synthesize HAP through the acylation of phenol. In this work, ZnO supported MgF 2 (ZnO/MgF 2 ) catalyst was prepared using an impregnation technique. Numerous ZnO were used to obtain an optimum condition of ZnO/MgF 2 . The as-prepared catalyst was then physico-chemically characterrized using various techniques. Subsequently, the catalytic activity of samples was examined for HAP generation through the acylation of phenol. 2. Experimental Synthesis of ZnO ZnO was synthesized according to Lin and Li23 with few modification. Generally, a precursor of Zn(CH 3 COO) 2 ·2H 2 O powder was dissolved in 20 mL of distilled water and homogeneously stirred at 80℃ until white slurry formed. Then, the white precipitate was dried in oven for 18 h. The dried precipitate was then calcined at 400℃ fo 4 h with the heating rate of 2℃/min. Synthesis of ZnO/MgF2 Catalyst ZnO supported MgF2 catalyst (ZnO/MgF¬2) was prepared through an impregnation method with various amount of Zn (2.5; 5; 7.5; 10 and 15% w/w). MgF2 powder was dissolved in 20 mL Zn(CH3COO)2 and homogeneously stirred at 80℃ until white slurry formed. The obtained white precipitate was filtered, washed with distilled water and dried at 100℃. The dried powder was grounded and calcined at 400℃ with the heating rate of 2℃/min. Catalyst Characterization The XRD characterization were performed by XRD Philips X-Pert using Cu Kα (1.54056Å) radiation, in the 2θ range of 20–90° with interval 0,05°. The acidity of samples was determined by pyridine adsorption FTIR method. The samples were poured 30 µL of pyridine. After that, it was heated for 3 hours at 150℃ under N 2 condition. The FTIR spectra of pyridine adsorbed samples were recorded and analyzed at wave numbers 1400–1750 cm-1 after cooling. The S BET surface area of the samples were measured by the nitrogen adsorption-desorption isotherm method at -196℃ using Quantachrome Nova. The samples were degassed with nitrogen at flow rate of 30 cm3/minute at 150℃ for 3 h. The morphology of the samples were observed by scanning electron microscopy (SEM) equipped with energy dispersive X-ray analysiss (EDX). Catalytic Test The acylation of phenol with acetic acid was carried out in a reflux fixed bed. Typically, 10 mg of the catalysts was placed in the boiling flask three neck containing of phenol and acetic acid. The ratio of phenol to aceting acid (3:1; 2:1; 1:1 and 1:3) and reaction time (60; 90; 120; 150 and 180 min) were assessed to obtain the optimum condition of the reaction. Subsequently, the obtained products were analyzed by using High Liquid Chromatography Agilent 11 using Lichrospher RP-18 5 µm column equipped with a UV detector. The analysis was carried out under 1 atm at 30℃ and the eluent was H 2 O (containing 0.5% acetate): methanol: ACN (acetonitrile) with a ratio of 60: 30: 10. 3. Result and Discussion Catalyst Characterization X-ray diffraction pattern of ZnO, MgF 2 and ZnO/MgF 2 samples were shown in Fig. 1. The XRD pattern was in accordance with JCPDS-International Centre of Diffraction Data PCPDFWIN. The characteristic peaks of the ZnO were at 31,78; 34,44; 36,27; 56,62° (Fig. 1a). In additon, peaks at 27,2; 40,35 dan 53,45° were associated to MgF 2 samples (Fig. 1b). Furthermore, the XRD pattern of ZnO/MgF 2 samples, showed a combination peaks between the peak of ZnO and MgF 2 where the characteristic peaks of MgF 2 were higher than ZnO. The characteristic peaks of ZnO increased upon increasing the ZnO percentages, as can be seen at peaks 31,78; 34,44; 36,27; 56,62° in all ZnO/MgF 2 samples (Fig. 1c-1g). This implies that the ZnO was successfully impregnated to MgF 2 catalyst. Furthermore, the surface acid sites of samples were assessed by FTIR spectroscopy using adsorbed pyridine samples, as shown in Fig. 2. The pyridinium ion shows absorption bands at 1578 cm -1 . Generally, pyridine coordinately bonded with the surface of the catalyst via Lewis acid sites and generated a characteristic bands at 1452 cm -1 [23], [25]. The bands at 1445-1462 cm -1 and 1608-1620 cm -1 generated a characteristic from pyridine adsorbed on Lewis and Brønsted acid sites, respectively on ZnO/MgF 2 samples [25], [26]. The pyridine absorption bands at 1491-1500 cm -1 indicate the presence of association peaks between Lewis and Brønsted acid sites [23], [26]. ZnO/MgF 2 samples have more acid sites than MgF 2 . Lewis and Brønsted acid peaks on all ZnO/MgF 2 samples increase with increasing amount of ZnO impregnated on MgF 2 . Furthermore, the surface area of the samples was measured using BET method and is summarized in Table 1. It can be seen that the surface area of the catalys decreased after addition of ZnO impregnation. This is in accordance with previously reported by Alam, M. et al. where the impregnation of Ni in SiO 2 could the decrease the surface area of the catalyst was due to the entry of Ni into SiO 2 [27]. Impregnation of ZnO on the surface of MgF 2 resulted in pore closure of MgF 2 by ZnO. Table 1 The result of surface area measurement Catalyst S BET (m 2 /g) MgF 2 24,05 ZnO - 2,5% ZnO/MgF 2 9,31 5% ZnO/MgF 2 8,05 7,5% ZnO/MgF 2 7,43 10% ZnO/MgF 2 7,21 15% ZnO/MgF 2 5,44 The nitrogen adsorption-desorption isotherm pattern from MgF 2 and ZnO/MgF 2 were shown in Fig. 3. Based on the IUPAC (International Union in Pure and Applied Chemistry) classification, all samples show type IV isothermal adsorption patterns. All samples have H1 hysteresis which indicates the presence of specific narrow neck pores [24]. Catalytic Test Phenol acylation reaction is the process of introducing acyl groups into aromatic rings in phenol. Acetic acid was chosen because acetic acid has more advantages compared to other acyl source such as acyl cholride and acetic anhydride[28]. According to Chandra et al.[29], metal oxide, ZnO, is a good catalyst for the acylation of alcohol reaction, because Zn 2+ is a stable Lewis acid, there is no redox reaction.[30] The catalytic test was initiated to obtain the optimum conditions of the reaction including reaction time and mol ratio of the solutions (phenol and acetic acid). All optimization of the reaction conditions was carried out using MgF 2 catalyst. The optimization of reaction times (60, 90, 120, 150 and 180 minutes) and ratio of phenol and acetic acid (3:1, 2:1, 1:1, 1:2 and 1:3) was carried out with a reaction of 20 mmol of phenol and acetic acid at 70℃. The highest phenol conversion was obtained with a reaction time of 150 minutes and ratio 1:1 with a conversion value of 68.19%. Furthermore, the obtained optimum conditions were used for the catalytic test for synthesized catalysts. In this study, the main products were p-HAP and PA. This reaction was in accordance with the study of Padró and Apesteguia[7] which mentioned that in the phenol acylation reaction with liquid phase produced p-HAP as the main product. The yield of the p-HAP and PA was the total moles of p-HAP and PA, respectively. However, the other products were considered as different moles between phenol reacting with p-HAP and PA. The results of the catalysis test obtained from the analysis using HPLC are presented in Fig. 6. The impregnation ZnO to MgF 2 catalyst (ZnO/MgF 2 ) increase the phenol conversion with an optimum value of 85.36%. 7.5% ZnO/MgF 2 catalyst can increase the phenol conversion until 8 times compared to reaction without catalyst. It shows that the ZnO/MgF 2 catalyst was active for the acylation of phenols. The yield of p -HAP and PA over ZnO/MgF 2 catalysts were greater than pure ZnO or MgF 2 catalyst. The yield of the p -HAP and PA with ZnO catalyst were 48.85% and 14.52% respectively, meanwhile the MgF 2 catalysts were 42.46% and 17.47% respectively. However, ZnO/MgF 2 catalysts could increase the yield of p -HAP and PA. The greatest yield of p -HAP (56.06%) and PA (23.40%) was obtained in the presence of 7.5% ZnO/MgF 2 catalyst. The selectivity calculation of each catalyst is showed in Fig. 7. The presence of 2.5% ZnO/MgF 2 catalyst increase the selectivity of p-HAP until 71.20%. Meanwhile, the 7.5% ZnO/MgF 2 increase the selectivity of PA until 26.47%. From the observations, it turned out that phenol conversion had the same tendency as acidity. This showed that acidity affected the percentage of phenol conversion. This phenomenon is in accordance with Kobayashi et al.[31] where the highest conversion was obtained by the Hf (OTf) 4 catalyst due to its highest acidity. In addition, the acidity properties of the catalyst also affected the phenol conversion. Specifically, the acidity of Lewis catalyst influenced the yield of p-HAP, while the acidity of Brønsted catalyst influenced the outcome of the PA product. This is supported by Naeimi et al.[10] which reported that the formation of p-HAP could occur in the presence of Lewis acid sites from solid catalysts. This in line with this study where the tendency of the Brønsted acidity of the ZnO/MgF 2 catalyst was the identical as that of the PA formation. The observations showed that the catalyst crystallinity was inversely proportional to p-HAP selectivity. Based on the discussion, it can be concluded that the formation of products was influenced by the acidity of the catalyst. In the phenol acylation reaction, there was a process of introducing an acyl group from the acylating agent to phenol. Neves, I., et al.[32] suggested that the mechanism of formation of HAP and PA products occured through reactant activation by the catalyst acid site. In this study the mechanism for forming p -HAP and PA is presented in Fig 6. The acetylating agent, acetic acid, reacted with the catalyst acid sites of both Lewis and Brønsted to form acylium ions (CH 3 CO + ) (Fig 8.A and Fig 9.A) which acted as electrophiles which would undergo substitution on phenols. During the formation of acylium ions occured, phenol was activated on the catalyst. This activation process converted phenols to nucleophiles which could bind to electrophiles. In the formation of p -HAP, phenols were activated on the Lewis acid site of the catalyst (Fig 8.A and Fig 9.A) forming phenol which had two poles, positive and negative. The negative pole of phenol attacked the acylium ion (Fig 8.B). Then the OH group from the acetic acid (still present in the catalyst) attacked the H atom in phenol (Fig 8.C) which then produced p -HAP (Fig 8.D). Brønsted acid site (Fig. 9.B). This caused the free electron pair OH group in phenol to react with acylium ions (Fig. 9.B) followed by the OH group attack of acetic acid which was still present on the catalyst against the H atom in the OH phenol group (Fig. 9.C). Furthermore, the formation of PA (Fig 9.D). In the mechanism of formation of both p -HAP and PA, the catalyst used can be formed again together with the formation of H 2 O by products. Acylium ion attack on the formation of p -HAP included in C-acylation, while in the formation of PA included in O-acylation. 4. Conclusion Heterogeneous catalysts of ZnO, MgF 2 and ZnO/MgF 2 have been successfully synthesized by using thermal decomposition, sol gel and impregnation methods, respectively. The smaller amount of Zn impregnated on MgF2 showed a greater the surface area, with S BET of 9.44 m2/g. Addition of the amount of Zn on MgF 2 affected the yield of p-HAP and PA. Conversion, yield and selectivity of p-HAP and PA were influenced by the acidity of the ZnO/MgF 2 catalyst where the formation of p-HAP was influenced by the Lewis acid site, while the formation of PA is influenced by the Brønsted acid site. The 7.5% ZnO/MgF 2 catalyst had the highest catalytic activity of the phenol conversion with the value of 85.36%. The formation p-HAP and PA products were 56.06 and 23.40 %, respectively. The highest p-HAP selectivity (71.20%) was achieved over 2.5% ZnO/MgF2 catalyst, while the highest PA selectivity (27.41%) was achieved by 7.5% ZnO/MgF2 catalyst. Declarations CRediT Authorship Contribution Statement Ika Fitri Ulfindrayani: Methodology, Validation, Investigation, Writing-Original Draft Preparation; Irmina Kris Murwani: Supervision, Conceptualization, Writing-Reviewing, Editing and Funding; Eko Sri Kunarti: Conceptualization, Editing; Harsasi Setyawati: Validation, Investigation; Afifah Rosyidah: Validation, Investigation. Qurrota A’yuni: formal analysis, writing, investigation, Abdul Wafi: validation, investigation, writing (review and editing). Eka Cahya Muliawati: Review and editing, writing. Acknowledgments The authors would like to acknowledge for financial support provided by The Ministry of Research, Technology and Higher Education of the Republic of Indonesia. Funding This work was supported by Directorate of Research and Community Service, Directorate General of Research and Development, The Ministry of Research, Technology and Higher Education of the Republic of Indonesia (Kemenristekdikti) with grant number of 6/E/KPT/2019 and 5/E1/KP.PTNBH/2019, March 29, 2019). Conflicts of Interest: The authors declare no conflict of interest. References Youn SW, Cho CG (2021) Transition-metal-catalyzedortho-selective C-H functionalization reactions of free phenols. Org Biomol Chem 19(23):5028–5047. 10.1039/d1ob00506e R. Roswanda, A. D. Sirampun, R. R. Mukti, and D. Mujahidin, A straightforward selective acylation of phenols over ZSM-5 towards making paracetamol precursors, Bull. Chem. React. Eng. & Catal. , vol. 13, no. 3, pp. 573–587, 2018, doi: 10.9767/bcrec.13.3.2856.573-587 Hu W, Zhang Z, Li L, Ding Y, An J (August, 2019) Preparation of electrospun SnO2 carbon nanofiber composite for ultra-sensitive detection of APAP and p-Hydroxyacetophenone. 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Cite Share Download PDF Status: Published Journal Publication published 16 Feb, 2026 Read the published version in Transition Metal Chemistry → Version 1 posted Editorial decision: Revision requested 14 Oct, 2025 Reviews received at journal 27 Sep, 2025 Reviewers agreed at journal 18 Sep, 2025 Reviews received at journal 16 Sep, 2025 Reviewers agreed at journal 16 Sep, 2025 Reviewers agreed at journal 16 Sep, 2025 Reviewers invited by journal 16 Sep, 2025 Editor assigned by journal 16 Sep, 2025 Submission checks completed at journal 16 Sep, 2025 First submitted to journal 11 Sep, 2025 You are reading this latest preprint version Research Square lets you share your work early, gain feedback from the community, and start making changes to your manuscript prior to peer review in a journal. As a division of Research Square Company, we’re committed to making research communication faster, fairer, and more useful. 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Also discoverable on Platform About Our Team In Review Editorial Policies Advisory Board Help Center Resources Author Services Accessibility API Access RSS feed Manage Cookie Preferences © Research Square 2026 | ISSN 2693-5015 (online) Privacy Policy Terms of Service Do Not Sell My Personal Information {"props":{"pageProps":{"initialData":{"identity":"rs-7593364","acceptedTermsAndConditions":true,"allowDirectSubmit":false,"archivedVersions":[],"articleType":"Research Article","associatedPublications":[],"authors":[{"id":517880587,"identity":"38fe6825-fc88-459c-a6a1-1943a3776183","order_by":0,"name":"Ika Fitri Ulfindrayani","email":"","orcid":"","institution":"Universitas Negeri Surabaya","correspondingAuthor":false,"prefix":"","firstName":"Ika","middleName":"Fitri","lastName":"Ulfindrayani","suffix":""},{"id":517880588,"identity":"220d1156-3370-4f55-a20e-d8656caf9774","order_by":1,"name":"Irmina Kris 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1","display":"","copyAsset":false,"role":"figure","size":895701,"visible":true,"origin":"","legend":"\u003cp\u003eXRD pattern of (a) ZnO, (b) MgF\u003csub\u003e2\u003c/sub\u003e, (c) 2,5% ZnO/MgF\u003csub\u003e2\u003c/sub\u003e, (d) 5% ZnO/MgF\u003csub\u003e2\u003c/sub\u003e, (e) 7,5% ZnO/MgF\u003csub\u003e2\u003c/sub\u003e, (f) 10% ZnO/MgF\u003csub\u003e2\u003c/sub\u003e and (g) 15% ZnO/MgF\u003csub\u003e2\u003c/sub\u003e\u003c/p\u003e","description":"","filename":"Picture1.png","url":"https://assets-eu.researchsquare.com/files/rs-7593364/v1/3cd8f741be4fa39b136b121d.png"},{"id":92111407,"identity":"794edf34-6f03-472a-9cde-f79f80b62ad0","added_by":"auto","created_at":"2025-09-24 18:27:30","extension":"jpg","order_by":2,"title":"Figure 2","display":"","copyAsset":false,"role":"figure","size":77255,"visible":true,"origin":"","legend":"\u003cp\u003eFTIR spectra of pyridine chemisorpstion of (a) ZnO, (b) MgF\u003csub\u003e2\u003c/sub\u003e, (c) 2,5% ZnO/MgF\u003csub\u003e2\u003c/sub\u003e, (d) 5% ZnO/MgF\u003csub\u003e2\u003c/sub\u003e, (e) 7,5% ZnO/MgF\u003csub\u003e2\u003c/sub\u003e, (f) 10% ZnO/MgF\u003csub\u003e2\u003c/sub\u003e and (g) 15% ZnO/MgF\u003csub\u003e2\u003c/sub\u003e\u003c/p\u003e","description":"","filename":"Picture2.jpg","url":"https://assets-eu.researchsquare.com/files/rs-7593364/v1/872917b73e38d1aee0ea46d6.jpg"},{"id":92111408,"identity":"49fce275-79e1-46e5-83b2-a9bdd8c0c163","added_by":"auto","created_at":"2025-09-24 18:27:30","extension":"jpg","order_by":3,"title":"Figure 3","display":"","copyAsset":false,"role":"figure","size":98778,"visible":true,"origin":"","legend":"\u003cp\u003eAdsorption-desorption isotherm of (a) MgF\u003csub\u003e2\u003c/sub\u003e ; (b) 2.5% ZnO/MgF\u003csub\u003e2\u003c/sub\u003e; (c) 5% ZnO/MgF\u003csub\u003e2\u003c/sub\u003e; (d) 7.5% ZnO/MgF\u003csub\u003e2\u003c/sub\u003e; (e) 10% ZnO/MgF\u003csub\u003e2\u003c/sub\u003e\u0026nbsp; dan (f) 15% ZnO/MgF\u003csub\u003e2\u003c/sub\u003e\u003c/p\u003e","description":"","filename":"Picture3.jpg","url":"https://assets-eu.researchsquare.com/files/rs-7593364/v1/704ec57dff1d223702c76c37.jpg"},{"id":92111409,"identity":"4d632f70-9486-4297-bfa4-99031458ebb9","added_by":"auto","created_at":"2025-09-24 18:27:30","extension":"png","order_by":4,"title":"Figure 4","display":"","copyAsset":false,"role":"figure","size":285153,"visible":true,"origin":"","legend":"\u003cp\u003eSEM image of 7,5% ZnO/MgF\u003csub\u003e2\u003c/sub\u003e catalyst\u003c/p\u003e","description":"","filename":"Picture4.png","url":"https://assets-eu.researchsquare.com/files/rs-7593364/v1/dd4946e48db94b42e41a5444.png"},{"id":92111671,"identity":"76bf2fcf-bb03-41d0-97fb-5cfc59589d1c","added_by":"auto","created_at":"2025-09-24 18:35:30","extension":"jpg","order_by":5,"title":"Figure 5","display":"","copyAsset":false,"role":"figure","size":31620,"visible":true,"origin":"","legend":"\u003cp\u003eEDX spectra of 7,5% ZnO/MgF\u003csub\u003e2\u003c/sub\u003e catalyst\u003c/p\u003e","description":"","filename":"Picture5.jpg","url":"https://assets-eu.researchsquare.com/files/rs-7593364/v1/be8e0b2e4dd68248dc3c742a.jpg"},{"id":92111416,"identity":"4c7e3458-7325-4f30-9769-4abcddea62c3","added_by":"auto","created_at":"2025-09-24 18:27:30","extension":"jpg","order_by":6,"title":"Figure 6","display":"","copyAsset":false,"role":"figure","size":66066,"visible":true,"origin":"","legend":"\u003cp\u003eSee image above for figure legend\u003c/p\u003e","description":"","filename":"Picture6.jpg","url":"https://assets-eu.researchsquare.com/files/rs-7593364/v1/01a67735ec6c0ff684363ea1.jpg"},{"id":92111672,"identity":"d32ca0d5-5281-45ba-b95e-591690fa4aee","added_by":"auto","created_at":"2025-09-24 18:35:30","extension":"jpg","order_by":7,"title":"Figure 7","display":"","copyAsset":false,"role":"figure","size":47185,"visible":true,"origin":"","legend":"\u003cp\u003eSee image above for figure legend\u003c/p\u003e","description":"","filename":"Picture7.jpg","url":"https://assets-eu.researchsquare.com/files/rs-7593364/v1/7e7506d2eb181d22d3bca2c2.jpg"},{"id":92112190,"identity":"f33d21fd-0480-4fa9-98aa-50bf1ef33ae6","added_by":"auto","created_at":"2025-09-24 18:43:30","extension":"png","order_by":8,"title":"Figure 8","display":"","copyAsset":false,"role":"figure","size":159196,"visible":true,"origin":"","legend":"\u003cp\u003eFormation reaction mechanism of p-HAP\u003c/p\u003e","description":"","filename":"Picture8.png","url":"https://assets-eu.researchsquare.com/files/rs-7593364/v1/fbf584cd7b2998f3b0cebebe.png"},{"id":92112185,"identity":"1a5b80b5-321d-43c9-8d2e-86a3a2d49c1e","added_by":"auto","created_at":"2025-09-24 18:43:30","extension":"png","order_by":9,"title":"Figure 9","display":"","copyAsset":false,"role":"figure","size":249882,"visible":true,"origin":"","legend":"\u003cp\u003eFormation reaction mechanism of o-HAP\u003c/p\u003e","description":"","filename":"Picture9.png","url":"https://assets-eu.researchsquare.com/files/rs-7593364/v1/e958fe22b727116bb60f0d9e.png"},{"id":103252961,"identity":"0b3b39a3-675a-4b31-9d13-fa6b632474f4","added_by":"auto","created_at":"2026-02-23 16:16:48","extension":"pdf","order_by":0,"title":"","display":"","copyAsset":false,"role":"manuscript-pdf","size":2421476,"visible":true,"origin":"","legend":"","description":"","filename":"manuscript.pdf","url":"https://assets-eu.researchsquare.com/files/rs-7593364/v1/e3c599d5-eb9e-42a5-9776-050539477744.pdf"}],"financialInterests":"No competing interests reported.","formattedTitle":"\u003cp\u003e\u003cstrong\u003eSynthesis and Characterization of Pure ZnO and ZnO Supported MgF\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003e2\u003c/strong\u003e\u003c/sub\u003e\u003cstrong\u003e for Catalytic Acylation of Phenol\u003c/strong\u003e\u003c/p\u003e","fulltext":[{"header":"1. Introduction","content":"\u003cp\u003ePhenol and its derivatives have been massively used in pharmaceutical field.[\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e] For instance, o-HAP (orto-hydroxyacetophenone) and p-HAP (orto-hydroxyacetophenone) are examples of phenol\u0026rsquo;s derivatives widely used as precursor to produce aspirin and paracetamol. \u003cem\u003eo\u003c/em\u003e-HAP is intermediates in producing of 4-hydroxicoumarin and warfarin which are used as anticoagulant drugs in the therapy of thrombotic diseases.[\u003cspan citationid=\"CR2\" class=\"CitationRef\"\u003e2\u003c/span\u003e] Meanwhile, \u003cem\u003ep\u003c/em\u003e-HAP is used in a process to obtain paracetamol.[\u003cspan citationid=\"CR3\" class=\"CitationRef\"\u003e3\u003c/span\u003e] HAP can be synthesis through phenol acylation via Fries rearrangement. Fries rearrangement is carried out in the presence of acid catalysts[\u003cspan citationid=\"CR4\" class=\"CitationRef\"\u003e4\u003c/span\u003e] such as ZnCl\u003csub\u003e2\u003c/sub\u003e[\u003cspan citationid=\"CR5\" class=\"CitationRef\"\u003e5\u003c/span\u003e], [\u003cspan citationid=\"CR6\" class=\"CitationRef\"\u003e6\u003c/span\u003e] to improve the yield of HAP.[\u003cspan citationid=\"CR7\" class=\"CitationRef\"\u003e7\u003c/span\u003e]\u003c/p\u003e\u003cp\u003eHowever, this synthesis approach is far from an environmental friendly due to its toxicity and corrosive properties. In addition this method requires a large amount of catalyst and difficult separation process between catalysts and products.[\u003cspan citationid=\"CR8\" class=\"CitationRef\"\u003e8\u003c/span\u003e], [\u003cspan citationid=\"CR9\" class=\"CitationRef\"\u003e9\u003c/span\u003e] For these reasons, the synthesis of HAP has shifted by using solid catalyst because it is easy to separate the final product and catalyst.[\u003cspan citationid=\"CR10\" class=\"CitationRef\"\u003e10\u003c/span\u003e], [\u003cspan citationid=\"CR11\" class=\"CitationRef\"\u003e11\u003c/span\u003e] Metal oxide has been widely used in the synthesis of HAP due to its has high acidity, rapid reaction, easy reaction conditions and environmental friendly.[\u003cspan citationid=\"CR2\" class=\"CitationRef\"\u003e2\u003c/span\u003e], [\u003cspan citationid=\"CR3\" class=\"CitationRef\"\u003e3\u003c/span\u003e], [\u003cspan citationid=\"CR12\" class=\"CitationRef\"\u003e12\u003c/span\u003e] Tamaddon et al.[\u003cspan citationid=\"CR12\" class=\"CitationRef\"\u003e12\u003c/span\u003e] reported that the most efficient metal oxide for synthesis of hydroxyacetophenone is zinc oxide (ZnO).\u003c/p\u003e\u003cp\u003eMany research has proven that ZnO has good ability as a catalyst or catalyst support.[\u003cspan additionalcitationids=\"CR14 CR15 CR16 CR17 CR18 CR19\" citationid=\"CR13\" class=\"CitationRef\"\u003e13\u003c/span\u003e]\u0026ndash;[\u003cspan citationid=\"CR20\" class=\"CitationRef\"\u003e20\u003c/span\u003e]. In 2005, Sarvari, M. H. and Sharghi, H. conducted phenol acylation reaction with ZnO catalyst at room temperature and solvent free conditions which achieved a yield of 94%.[\u003cspan citationid=\"CR21\" class=\"CitationRef\"\u003e21\u003c/span\u003e] The use of ZnO in other phenol acylation reactions was also carried out by Moghaddam, F. M. and Saeidian, H. (2007).[\u003cspan citationid=\"CR22\" class=\"CitationRef\"\u003e22\u003c/span\u003e] In their research, Moghaddam, F. M. and Saeidian, H. reacted phenol with acetyl chloride at room temperature for 5 minutes and the yield obtained was 95%. However, the reaction that occurs in some studies with ZnO catalysts is an O acylation reaction. In the acylation of phenol, there are two kinds of acylation that may occur, namely C acylation and O acylation. In the C acylation process, acylation on phenol directly produces HAP compounds while in O acylation, HAP compounds are not directly formed but through phenyl acetate intermediates which can later produce HAP compounds through Fries rearrangement. According to Padr\u0026oacute; and Apestegu\u0026iacute;a (2004), this Fries rearrangement requires an acidic catalyst so that the formation of HAP compounds through phenol acylation reactions can take place with the help of acidic catalysts.\u003c/p\u003e\u003cp\u003eIn the phenol acylation reaction, the acidity of a catalyst affects the products produced.[\u003cspan citationid=\"CR7\" class=\"CitationRef\"\u003e7\u003c/span\u003e], [\u003cspan citationid=\"CR23\" class=\"CitationRef\"\u003e23\u003c/span\u003e] Therefore, in this study it is necessary to increase the acidity of the ZnO catalyst. According to Wojciechowska et al.[\u003cspan citationid=\"CR24\" class=\"CitationRef\"\u003e24\u003c/span\u003e], the increasing of catalyst acidity can be achieved by providing catalyst support because it can affect the active site of the catalyst during the catalysis process. MgF\u003csub\u003e2\u003c/sub\u003e has conditions as a catalyst support such as high thermal stability (500\u0026deg;C), inert surface, high hardness and large surface area. Besides that, the addition of catalyst support can increase the surface area of the catalyst. In this research, ZnO supported MgF\u003csub\u003e2\u003c/sub\u003e (ZnO/MgF\u003csub\u003e2\u003c/sub\u003e) catalyst will be used to synthesize HAP through the acylation of phenol.\u003c/p\u003e\u003cp\u003eIn this work, ZnO supported MgF\u003csub\u003e2\u003c/sub\u003e (ZnO/MgF\u003csub\u003e2\u003c/sub\u003e) catalyst was prepared using an impregnation technique. Numerous ZnO were used to obtain an optimum condition of ZnO/MgF\u003csub\u003e2\u003c/sub\u003e. The as-prepared catalyst was then physico-chemically characterrized using various techniques. Subsequently, the catalytic activity of samples was examined for HAP generation through the acylation of phenol.\u003c/p\u003e"},{"header":"2. Experimental","content":"\u003cp\u003e\u003cb\u003eSynthesis of ZnO\u003c/b\u003e\u003c/p\u003e\u003cp\u003eZnO was synthesized according to Lin and Li23 with few modification. Generally, a precursor of Zn(CH\u003csub\u003e3\u003c/sub\u003eCOO)\u003csub\u003e2\u003c/sub\u003e\u0026middot;2H\u003csub\u003e2\u003c/sub\u003eO powder was dissolved in 20 mL of distilled water and homogeneously stirred at 80℃ until white slurry formed. Then, the white precipitate was dried in oven for 18 h. The dried precipitate was then calcined at 400℃ fo 4 h with the heating rate of 2℃/min.\u003c/p\u003e\u003cp\u003e\u003cb\u003eSynthesis of ZnO/MgF2 Catalyst\u003c/b\u003e\u003c/p\u003e\u003cp\u003eZnO supported MgF2 catalyst (ZnO/MgF\u0026not;2) was prepared through an impregnation method with various amount of Zn (2.5; 5; 7.5; 10 and 15% w/w). MgF2 powder was dissolved in 20 mL Zn(CH3COO)2 and homogeneously stirred at 80℃ until white slurry formed. The obtained white precipitate was filtered, washed with distilled water and dried at 100℃. The dried powder was grounded and calcined at 400℃ with the heating rate of 2℃/min.\u003c/p\u003e\u003cp\u003e\u003cb\u003eCatalyst Characterization\u003c/b\u003e\u003c/p\u003e\u003cp\u003eThe XRD characterization were performed by XRD Philips X-Pert using Cu Kα (1.54056\u0026Aring;) radiation, in the 2θ range of 20\u0026ndash;90\u0026deg; with interval 0,05\u0026deg;.\u003c/p\u003e\u003cp\u003eThe acidity of samples was determined by pyridine adsorption FTIR method. The samples were poured 30 \u0026micro;L of pyridine. After that, it was heated for 3 hours at 150℃ under N\u003csub\u003e2\u003c/sub\u003e condition.\u003c/p\u003e\u003cp\u003eThe FTIR spectra of pyridine adsorbed samples were recorded and analyzed at wave numbers 1400\u0026ndash;1750 cm-1 after cooling.\u003c/p\u003e\u003cp\u003eThe S\u003csub\u003eBET\u003c/sub\u003e surface area of the samples were measured by the nitrogen adsorption-desorption isotherm method at -196℃ using Quantachrome Nova. The samples were degassed with nitrogen at flow rate of 30 cm3/minute at 150℃ for 3 h.\u003c/p\u003e\u003cp\u003eThe morphology of the samples were observed by scanning electron microscopy (SEM) equipped with energy dispersive X-ray analysiss (EDX).\u003c/p\u003e\u003cp\u003e\u003cb\u003eCatalytic Test\u003c/b\u003e\u003c/p\u003e\u003cp\u003eThe acylation of phenol with acetic acid was carried out in a reflux fixed bed. Typically, 10 mg of the catalysts was placed in the boiling flask three neck containing of phenol and acetic acid. The ratio of phenol to aceting acid (3:1; 2:1; 1:1 and 1:3) and reaction time (60; 90; 120; 150 and 180 min) were assessed to obtain the optimum condition of the reaction. Subsequently, the obtained products were analyzed by using High Liquid Chromatography Agilent 11 using Lichrospher RP-18 5 \u0026micro;m column equipped with a UV detector. The analysis was carried out under 1 atm at 30℃ and the eluent was H\u003csub\u003e2\u003c/sub\u003eO (containing 0.5% acetate): methanol: ACN (acetonitrile) with a ratio of 60: 30: 10.\u003c/p\u003e"},{"header":"3. Result and Discussion","content":"\u003cp\u003e\u003cstrong\u003eCatalyst Characterization\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eX-ray diffraction pattern of ZnO, MgF\u003csub\u003e2\u003c/sub\u003e and ZnO/MgF\u003csub\u003e2\u003c/sub\u003e samples were shown in Fig. 1. The XRD pattern was in accordance with JCPDS-International Centre of Diffraction Data PCPDFWIN. \u0026nbsp;The characteristic peaks of the ZnO were at 31,78; 34,44; 36,27; 56,62\u0026deg; (Fig. 1a). In additon, peaks at 27,2; 40,35 dan 53,45\u0026deg; were associated to MgF\u003csub\u003e2\u003c/sub\u003e samples (Fig. 1b). Furthermore, the XRD pattern of ZnO/MgF\u003csub\u003e2\u003c/sub\u003e samples, showed a combination peaks between the peak of ZnO and MgF\u003csub\u003e2\u003c/sub\u003e where the characteristic peaks of MgF\u003csub\u003e2\u003c/sub\u003e were higher than ZnO. The characteristic peaks of ZnO increased upon increasing the ZnO percentages, as can be seen at peaks 31,78; 34,44; 36,27; 56,62\u0026deg; in all ZnO/MgF\u003csub\u003e2\u003c/sub\u003e samples (Fig. 1c-1g). This implies that the ZnO was successfully impregnated to MgF\u003csub\u003e2\u003c/sub\u003e catalyst.\u0026nbsp;\u003c/p\u003e\n\u003cp\u003eFurthermore, the surface acid sites of samples were assessed by FTIR spectroscopy using adsorbed pyridine samples, as shown in Fig. 2. The pyridinium ion shows absorption bands at 1578 cm\u003csup\u003e-1\u003c/sup\u003e. Generally, pyridine coordinately bonded with the surface of the catalyst via Lewis acid sites and generated a characteristic bands at 1452 cm\u003csup\u003e-1\u003c/sup\u003e [23], [25]. The bands at 1445-1462 cm\u003csup\u003e-1\u003c/sup\u003e and 1608-1620 cm\u003csup\u003e-1\u003c/sup\u003e generated a characteristic from pyridine adsorbed on Lewis and Br\u0026oslash;nsted acid sites, respectively on ZnO/MgF\u003csub\u003e2\u003c/sub\u003e samples [25], [26]. The pyridine absorption bands at 1491-1500 cm\u003csup\u003e-1\u003c/sup\u003e indicate the presence of association peaks between Lewis and Br\u0026oslash;nsted acid sites [23], [26]. ZnO/MgF\u003csub\u003e2\u003c/sub\u003e samples have more acid sites than MgF\u003csub\u003e2\u003c/sub\u003e. Lewis and Br\u0026oslash;nsted acid peaks on all ZnO/MgF\u003csub\u003e2\u003c/sub\u003e samples increase with increasing amount of ZnO impregnated on MgF\u003csub\u003e2\u003c/sub\u003e.\u003c/p\u003e\n\u003cp\u003eFurthermore, the surface area of the samples was measured using BET method and is summarized in Table 1. It can be seen that the surface area of the catalys decreased after addition of ZnO impregnation. This is in accordance with previously reported by Alam, M. et al. where the impregnation of Ni in SiO\u003csub\u003e2\u003c/sub\u003e could the decrease the surface area of the catalyst was due to the entry of Ni into SiO\u003csub\u003e2\u003c/sub\u003e [27]. Impregnation of ZnO on the surface of MgF\u003csub\u003e2\u003c/sub\u003e resulted in pore closure of MgF\u003csub\u003e2\u003c/sub\u003e by ZnO.\u0026nbsp;\u003c/p\u003e\n\u003cp\u003eTable 1 The result of surface area measurement\u0026nbsp;\u003c/p\u003e\n\u003ctable border=\"1\" cellspacing=\"0\" cellpadding=\"0\" width=\"216\"\u003e\n \u003ctbody\u003e\n \u003ctr\u003e\n \u003ctd valign=\"top\" style=\"width: 63.8889%;\"\u003e\n \u003cp\u003e\u003cstrong\u003eCatalyst\u003c/strong\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 36.1111%;\"\u003e\n \u003cp\u003e\u003cstrong\u003eS\u003csub\u003eBET\u003c/sub\u003e\u003c/strong\u003e\u003c/p\u003e\n \u003cp\u003e\u003cstrong\u003e(m\u003csup\u003e2\u003c/sup\u003e/g)\u003c/strong\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd valign=\"top\" style=\"width: 63.8889%;\"\u003e\n \u003cp\u003e\u003cstrong\u003eMgF\u003csub\u003e2\u003c/sub\u003e\u003c/strong\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 36.1111%;\"\u003e\n \u003cp\u003e24,05\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd valign=\"top\" style=\"width: 63.8889%;\"\u003e\n \u003cp\u003e\u003cstrong\u003eZnO\u003c/strong\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 36.1111%;\"\u003e\n \u003cp\u003e-\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd valign=\"top\" style=\"width: 63.8889%;\"\u003e\n \u003cp\u003e\u003cstrong\u003e2,5% ZnO/MgF\u003csub\u003e2\u003c/sub\u003e\u003c/strong\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 36.1111%;\"\u003e\n \u003cp\u003e9,31\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd valign=\"top\" style=\"width: 63.8889%;\"\u003e\n \u003cp\u003e\u003cstrong\u003e5% ZnO/MgF\u003csub\u003e2\u003c/sub\u003e\u003c/strong\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 36.1111%;\"\u003e\n \u003cp\u003e8,05\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd valign=\"top\" style=\"width: 63.8889%;\"\u003e\n \u003cp\u003e\u003cstrong\u003e7,5% ZnO/MgF\u003csub\u003e2\u003c/sub\u003e\u003c/strong\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 36.1111%;\"\u003e\n \u003cp\u003e7,43\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd valign=\"top\" style=\"width: 63.8889%;\"\u003e\n \u003cp\u003e\u003cstrong\u003e10% ZnO/MgF\u003csub\u003e2\u003c/sub\u003e\u003c/strong\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 36.1111%;\"\u003e\n \u003cp\u003e7,21\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd valign=\"top\" style=\"width: 63.8889%;\"\u003e\n \u003cp\u003e\u003cstrong\u003e15% ZnO/MgF\u003csub\u003e2\u003c/sub\u003e\u003c/strong\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 36.1111%;\"\u003e\n \u003cp\u003e5,44\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003c/tbody\u003e\n\u003c/table\u003e\n\u003cp\u003eThe nitrogen adsorption-desorption isotherm pattern from MgF\u003csub\u003e2\u003c/sub\u003e and ZnO/MgF\u003csub\u003e2\u003c/sub\u003e were shown in Fig. 3. Based on the IUPAC (International Union in Pure and Applied Chemistry) classification, all samples show type IV isothermal adsorption patterns. All samples have H1 hysteresis which indicates the presence of specific narrow neck pores [24].\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eCatalytic Test\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003ePhenol acylation reaction is the process of introducing acyl groups into aromatic rings in phenol. Acetic acid was chosen because acetic acid has more advantages compared to other acyl source such as acyl cholride and acetic anhydride[28]. According to Chandra et al.[29], metal oxide, ZnO, is a good catalyst for the acylation of alcohol reaction, because Zn\u003csup\u003e2+\u003c/sup\u003e is a stable Lewis acid, there is no redox reaction.[30]\u003c/p\u003e\n\u003cp\u003eThe catalytic test was initiated to obtain the optimum conditions of the reaction including reaction time and mol ratio of the solutions (phenol and acetic acid). All optimization of the reaction conditions was carried out using MgF\u003csub\u003e2\u0026nbsp;\u003c/sub\u003ecatalyst. The optimization of reaction times (60, 90, 120, 150 and 180 minutes) and ratio of phenol and acetic acid (3:1, 2:1, 1:1, 1:2 and 1:3) was carried out with a reaction of 20 mmol of phenol and acetic acid at 70℃. The highest phenol conversion was obtained with a reaction time of 150 minutes and ratio 1:1 with a conversion value of 68.19%.\u003c/p\u003e\n\u003cp\u003eFurthermore, the obtained optimum conditions were used for the catalytic test for synthesized catalysts. In this study, the main products were p-HAP and PA. This reaction was in accordance with the study of Padr\u0026oacute; and Apesteguia[7] which mentioned that in the phenol acylation reaction with liquid phase produced p-HAP as the main product. The yield of the p-HAP and PA was the total moles of p-HAP and PA, respectively. However, the other products were considered as different moles between phenol reacting with p-HAP and PA. The results of the catalysis test obtained from the analysis using HPLC are \u0026nbsp;presented in Fig. 6.\u003c/p\u003e\n\u003cp\u003eThe impregnation ZnO to MgF\u003csub\u003e2\u003c/sub\u003e catalyst (ZnO/MgF\u003csub\u003e2\u003c/sub\u003e) increase the phenol conversion with an optimum value of 85.36%. 7.5% ZnO/MgF\u003csub\u003e2\u003c/sub\u003e catalyst can increase the phenol conversion until 8 times compared to reaction without catalyst. It shows that the ZnO/MgF\u003csub\u003e2\u0026nbsp;\u003c/sub\u003ecatalyst was active for the acylation of phenols. The yield of \u003cem\u003ep\u003c/em\u003e-HAP and PA over ZnO/MgF\u003csub\u003e2\u003c/sub\u003e catalysts were greater than pure ZnO or MgF\u003csub\u003e2\u003c/sub\u003e catalyst. The yield of the \u003cem\u003ep\u003c/em\u003e-HAP and PA with ZnO catalyst were 48.85% and 14.52% respectively, meanwhile the MgF\u003csub\u003e2\u003c/sub\u003e catalysts were 42.46% and 17.47% respectively. However, ZnO/MgF\u003csub\u003e2\u003c/sub\u003e catalysts could increase the yield of \u003cem\u003ep\u003c/em\u003e-HAP and PA. The greatest yield of \u003cem\u003ep\u003c/em\u003e-HAP (56.06%) and PA (23.40%) \u0026nbsp;was obtained in the presence of 7.5% ZnO/MgF\u003csub\u003e2\u003c/sub\u003e catalyst. The selectivity calculation of each catalyst is showed in Fig. 7. The presence of 2.5% ZnO/MgF\u003csub\u003e2\u003c/sub\u003e catalyst increase the selectivity of p-HAP until 71.20%. Meanwhile, the 7.5% ZnO/MgF\u003csub\u003e2\u003c/sub\u003e increase the selectivity of PA until 26.47%.\u003c/p\u003e\n\u003cp\u003eFrom the observations, it turned out that phenol conversion had the same tendency as acidity. This showed that acidity affected the percentage of phenol conversion. This phenomenon is in accordance with Kobayashi et al.[31] where the highest conversion was obtained by the Hf (OTf)\u003csub\u003e4\u0026nbsp;\u003c/sub\u003ecatalyst due to its highest acidity. In addition, the acidity properties of the catalyst also affected the phenol conversion. Specifically, the acidity of Lewis catalyst influenced the yield of p-HAP, while the acidity of Br\u0026oslash;nsted catalyst influenced the outcome of the PA product. This is supported by Naeimi et al.[10] which reported that the formation of p-HAP could occur in the presence of Lewis acid sites from solid catalysts. This in line with this study where the tendency of the Br\u0026oslash;nsted acidity of the ZnO/MgF\u003csub\u003e2\u003c/sub\u003e catalyst was the identical as that of the PA formation. The observations showed that the catalyst crystallinity was inversely proportional to p-HAP selectivity.\u003c/p\u003e\n\u003cp\u003eBased on the discussion, it can be concluded that the formation of products was influenced by the acidity of the catalyst. In the phenol acylation reaction, there was a process of introducing an acyl group from the acylating agent to phenol. Neves, I., et al.[32] suggested that the mechanism of formation of HAP and PA products occured through reactant activation by the catalyst acid site. In this study the mechanism for forming \u003cem\u003ep\u003c/em\u003e-HAP and PA is presented in Fig 6. The acetylating agent, acetic acid, reacted with the catalyst acid sites of both Lewis and Br\u0026oslash;nsted to form acylium ions (CH\u003csub\u003e3\u003c/sub\u003eCO\u003csup\u003e+\u003c/sup\u003e) (Fig 8.A and Fig 9.A) which acted as electrophiles which would undergo substitution on phenols. During the formation of acylium ions occured, phenol was activated on the catalyst. This activation process converted phenols to nucleophiles which could bind to electrophiles. In the formation of \u003cem\u003ep\u003c/em\u003e-HAP, phenols were activated on the Lewis acid site of the catalyst (Fig 8.A and Fig 9.A) forming phenol which had two poles, positive and negative. The negative pole of phenol attacked the acylium ion (Fig 8.B). Then the OH group from the acetic acid (still present in the catalyst) attacked the H atom in phenol (Fig 8.C) which then produced \u003cem\u003ep\u003c/em\u003e-HAP (Fig 8.D).\u003c/p\u003e\n\u003cp\u003eBr\u0026oslash;nsted acid site (Fig. 9.B). This caused the free electron pair OH group in phenol to react with acylium ions (Fig. 9.B) followed by the OH group attack of acetic acid which was still present on the catalyst against the H atom in the OH phenol group (Fig. 9.C). Furthermore, the formation of PA (Fig 9.D). In the mechanism of formation of both \u003cem\u003ep\u003c/em\u003e-HAP and PA, the catalyst used can be formed again together with the formation of H\u003csub\u003e2\u003c/sub\u003eO by products. Acylium ion attack on the formation of \u003cem\u003ep\u003c/em\u003e-HAP included in C-acylation, while in the formation of PA included in O-acylation.\u003c/p\u003e"},{"header":"4. Conclusion","content":"\u003cp\u003eHeterogeneous catalysts of ZnO, MgF\u003csub\u003e2\u003c/sub\u003e and ZnO/MgF\u003csub\u003e2\u003c/sub\u003e have been successfully synthesized by using thermal decomposition, sol gel and impregnation methods, respectively. The smaller amount of Zn impregnated on MgF2 showed a greater the surface area, with S\u003csub\u003eBET\u003c/sub\u003e of 9.44 m2/g. Addition of the amount of Zn on MgF\u003csub\u003e2\u003c/sub\u003e affected the yield of p-HAP and PA. Conversion, yield and selectivity of p-HAP and PA were influenced by the acidity of the ZnO/MgF\u003csub\u003e2\u003c/sub\u003e catalyst where the formation of p-HAP was influenced by the Lewis acid site, while the formation of PA is influenced by the Br\u0026oslash;nsted acid site. The 7.5% ZnO/MgF\u003csub\u003e2\u003c/sub\u003e catalyst had the highest catalytic activity of the phenol conversion with the value of 85.36%. The formation p-HAP and PA products were 56.06 and 23.40 %, respectively. The highest p-HAP selectivity (71.20%) was achieved over 2.5% ZnO/MgF2 catalyst, while the highest PA selectivity (27.41%) was achieved by 7.5% ZnO/MgF2 catalyst.\u003c/p\u003e"},{"header":"Declarations","content":"\u003cp\u003e\u003cstrong\u003eCRediT Authorship Contribution Statement\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eIka Fitri Ulfindrayani: Methodology, Validation, Investigation, Writing-Original Draft Preparation; Irmina Kris Murwani: Supervision, Conceptualization, Writing-Reviewing, Editing and Funding; Eko Sri Kunarti: Conceptualization, Editing; Harsasi Setyawati: Validation, Investigation; Afifah Rosyidah: Validation, Investigation. Qurrota A\u0026rsquo;yuni: formal analysis, writing, investigation, Abdul Wafi: validation, investigation, writing (review and editing). Eka Cahya Muliawati: Review and editing, writing.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eAcknowledgments\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eThe authors would like to acknowledge for financial support provided by The Ministry of Research, Technology and Higher Education of the Republic of Indonesia.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eFunding\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eThis work was supported by Directorate of Research and Community Service, Directorate General of Research and Development, The Ministry of Research, Technology and Higher Education of the Republic of Indonesia (Kemenristekdikti) with grant number of 6/E/KPT/2019 and 5/E1/KP.PTNBH/2019, March 29, 2019).\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eConflicts of Interest: \u003c/strong\u003eThe authors declare no conflict of interest.\u003c/p\u003e"},{"header":"References","content":"\u003col\u003e\u003cli\u003e\u003cspan\u003eYoun SW, Cho CG (2021) Transition-metal-catalyzedortho-selective C-H functionalization reactions of free phenols. 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J Chem Soc Chem Commun no. 6:717\u0026ndash;718. \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003e10.1039/C39940000717\u003c/span\u003e\u003cspan address=\"10.1039/C39940000717\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e\u003c/ol\u003e"}],"fulltextSource":"","fullText":"","funders":[],"hasAdminPriorityOnWorkflow":false,"hasManuscriptDocX":true,"hasOptedInToPreprint":true,"hasPassedJournalQc":"","hasAnyPriority":false,"hideJournal":false,"highlight":"","institution":"","isAcceptedByJournal":true,"isAuthorSuppliedPdf":false,"isDeskRejected":"","isHiddenFromSearch":false,"isInQc":false,"isInWorkflow":false,"isPdf":false,"isPdfUpToDate":true,"isWithdrawnOrRetracted":false,"journal":{"display":true,"email":"[email protected]","identity":"transition-metal-chemistry","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":false,"externalIdentity":"tmch","sideBox":"Learn more about [Transition Metal Chemistry](http://link.springer.com/journal/11243)","snPcode":"11243","submissionUrl":"https://submission.nature.com/new-submission/11243/3","title":"Transition Metal Chemistry","twitterHandle":"","acdcEnabled":true,"dfaEnabled":true,"editorialSystem":"em","reportingPortfolio":"Springer Hybrid","inReviewEnabled":true,"inReviewRevisionsEnabled":false},"keywords":"acylation of phenol, cactalyst, ZnO/MgF2, hydroxyacetophenone","lastPublishedDoi":"10.21203/rs.3.rs-7593364/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-7593364/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"\u003cp\u003eThe catalysts MgF\u003csub\u003e2\u003c/sub\u003e supported ZnO (0; 2.5; 5; 7.5; 10 and 15% \u003cem\u003ew\u003c/em\u003e/\u003cem\u003ew\u003c/em\u003e) were synthesized by sol-gel method. The structure of the catalysts were characterized by XRD. The acidity of the catalyst determined by pyridine-FTIR method showed that 7.5% ZnO/MgF\u003csub\u003e2\u003c/sub\u003e had the highest acidity. The surface area of the ZnO/MgF\u003csub\u003e2\u003c/sub\u003e was measured by N\u003csub\u003e2\u003c/sub\u003e adsorption-desorption method. The surface area of the ZnO/MgF2 catalysts decrease with the increase in Zn content. The measurement SBET of the catalysts was in range of 5,31 to 9,44 m\u003csup\u003e2\u003c/sup\u003e/g. The morphology of the catalyst was observed by Scanning Electron Microscope (SEM). The synthesized catalysts performance was tested in phenol acylation and were determined by High Performance Liquid Chromatography (HPLC), which the main products were \u003cem\u003ep\u003c/em\u003e-HAP (hydroxyacetophenone) and PA (phenyl acetate). The formation of \u003cem\u003ep\u003c/em\u003e-HAP was influenced by the Lewis acid site, while PA was influenced by the Br\u0026oslash;nsted acid site. The highest conversion was achieved 85.36% by 7.5% ZnO/MgF\u003csub\u003e2\u003c/sub\u003e, while the yields of the \u003cem\u003ep\u003c/em\u003e-HAP and PA were 56.06 and 23.40% respectively.\u003c/p\u003e","manuscriptTitle":"Synthesis and Characterization of Pure ZnO and ZnO Supported MgF2 for Catalytic Acylation of Phenol","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2025-09-24 18:27:25","doi":"10.21203/rs.3.rs-7593364/v1","editorialEvents":[{"type":"communityComments","content":0},{"type":"decision","content":"Revision requested","date":"2025-10-14T16:22:29+00:00","index":"","fulltext":""},{"type":"editorInvitedReview","content":"","date":"2025-09-27T11:02:05+00:00","index":"hide","fulltext":""},{"type":"reviewerAgreed","content":"6886799995721786149381284447412269748","date":"2025-09-18T10:27:16+00:00","index":"hide","fulltext":""},{"type":"editorInvitedReview","content":"","date":"2025-09-16T12:32:50+00:00","index":"hide","fulltext":""},{"type":"reviewerAgreed","content":"216722846476015583704318987359428463072","date":"2025-09-16T11:29:25+00:00","index":"hide","fulltext":""},{"type":"reviewerAgreed","content":"62793205025686315969105262715823419230","date":"2025-09-16T11:09:50+00:00","index":"hide","fulltext":""},{"type":"reviewersInvited","content":"","date":"2025-09-16T10:14:29+00:00","index":"","fulltext":""},{"type":"editorAssigned","content":"","date":"2025-09-16T10:07:05+00:00","index":"","fulltext":""},{"type":"checksComplete","content":"","date":"2025-09-16T08:23:22+00:00","index":"","fulltext":""},{"type":"submitted","content":"Transition Metal Chemistry","date":"2025-09-11T15:14:25+00:00","index":"","fulltext":""}],"status":"published","journal":{"display":true,"email":"[email protected]","identity":"transition-metal-chemistry","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":false,"externalIdentity":"tmch","sideBox":"Learn more about [Transition Metal Chemistry](http://link.springer.com/journal/11243)","snPcode":"11243","submissionUrl":"https://submission.nature.com/new-submission/11243/3","title":"Transition Metal Chemistry","twitterHandle":"","acdcEnabled":true,"dfaEnabled":true,"editorialSystem":"em","reportingPortfolio":"Springer Hybrid","inReviewEnabled":true,"inReviewRevisionsEnabled":false}}],"origin":"","ownerIdentity":"88de9db7-d234-4a87-a991-fc2cdcdcd62d","owner":[],"postedDate":"September 24th, 2025","published":true,"recentEditorialEvents":[],"rejectedJournal":[],"revision":"","amendment":"","status":"published-in-journal","subjectAreas":[],"tags":[],"updatedAt":"2026-02-23T16:16:14+00:00","versionOfRecord":{"articleIdentity":"rs-7593364","link":"https://doi.org/10.1007/s11243-025-00710-1","journal":{"identity":"transition-metal-chemistry","isVorOnly":false,"title":"Transition Metal Chemistry"},"publishedOn":"2026-02-16 15:58:19","publishedOnDateReadable":"February 16th, 2026"},"versionCreatedAt":"2025-09-24 18:27:25","video":"","vorDoi":"10.1007/s11243-025-00710-1","vorDoiUrl":"https://doi.org/10.1007/s11243-025-00710-1","workflowStages":[]},"version":"v1","identity":"rs-7593364","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-7593364","identity":"rs-7593364","version":["v1"]},"buildId":"8U1c8b4HqxoKbykW_rLl7","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}