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Efficient Synthesis of Methyl Methacrylate by One Step Oxidative catalysts Article Efficient Synthesis of Methyl Methacrylate by One Step Oxidative Esterification over Zn-Al-Mixed Oxides Supported Gold Nanocatalysts Huayin Li 1, Yuan Tan 1,* , Xingkun Chen 1, Wenshao Yang 1, Chuanqi Huang 1, Jie Li 1 and Yunjie Ding 1,2,3,* 1 Hangzhou Institute of Advanced studies, Zhejiang Normal University, Hangzhou 311231, China; [email protected] (H.L.); [email protected] (X.C.); [email protected] (W.Y.); [email protected] (C.H.); [email protected] (J.L.) 2 Dalian National Laboratory for Clean Energy, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China 3 The State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China * Correspondence: [email protected] (Y.T.); [email protected] (Y.D.); Tel.: +86-571-82257902 (Y.T.); +86-411-84379143 (Y.D.) Abstract: Methyl methacrylate (MMA) is an important monomer in fine chemicals. The synthesis of MMA by one-step oxidative esterification from methacrolein with methanol over a heterogeneous catalyst with high activity, selectivity and stability is highly desirable. Herein, Zn-Al-hydrotalcites 2+ 3+ (HTs)-supported atomically precise Au25 nanoclusters with different molar ratios of Zn /Al were prepared and used as the precursors for this reaction. They exhibited good performances in com- parison with the gold catalysts prepared by the deposition precipitation method. The structural and electronic properties were evaluated by various characterization technologies, including X-ray diffraction (XRD), high-resolution transmission electron microscopy (HRTEM), in situ diffuse re- Citation: Li, H.; Tan, Y.; Chen, X.; Yang, W.; Huang, C.; Li, J.; Ding, Y. flectance infrared Fourier-transform spectroscopy (DRIFTS) of CO adsorption, X-ray photoelectron Efficient Synthesis of Methyl spectroscopy (XPS), and CO2 temperature-programmed desorption (TPD). The combined charac- Methacrylate by One Step Oxidative terization results suggested that the adsorption property of gold and the basicity of the catalyst Esterification over Zn-Al-Mixed contributes to their high activities. Substrates extended experiments and stability tests implied the Oxides Supported Gold Nanocatalysts. potential application of Zn-Al-mixed oxides supported gold catalysts, which paves a new way for Catalysts 2021, 11, 162. https:// supported gold catalyst in the one-step oxidation esterification reaction. doi.org/10.3390/catal11020162 Keywords: gold cluster; hydrotalcite; methacrolein; methyl methacrylate; oxidative esterification Academic Editor: Werner Oberhauser Received: 18 December 2020 Accepted: 21 January 2021 Published: 25 January 2021 1. Introduction Publisher’s Note: MDPI stays neutral Methyl methacrylate (MMA) is an important monomer for the synthesis of poly- with regard to jurisdictional claims in methyl methacrylate (PMMA), which is widely used for producing acrylic plastic [1]. published maps and institutional affil- A recent analysis originated from the global MMA market indicated that the demand for iations. MMA may reach $9.8 billion by 2027 [2]. Thus, a noteworthy growth in MMA monomers will appear in the next several years. Traditionally, the dominant industrial process for the synthesis of MMA has been the acetone cyanohydrin (ACH) route [3], in which acetone and hydrocyanic acid are used as the raw materials. At the same time, the ACH process involves environmentally unfriendly issues that employ strong sulfuric acid as a catalyst Copyright: © 2021 by the authors. Licensee MDPI, Basel, Switzerland. and inevitably generate ammonium bisulfate waste [3,4]. This article is an open access article Currently, isobutene (IB) oxidation routes that stem from isobutene and C4 ingredients distributed under the terms and for producing MMA are attracting great interest due to the economic and environmen- conditions of the Creative Commons tal preponderance [5,6]. In these processes, isobutene is first oxidized to methacrolein Attribution (CC BY) license (https:// (MAL) and then oxidized to methacrylic acid (MAA), followed by esterification of MAA creativecommons.org/licenses/by/ to MMA [5]. Instead, MAL could also react with methanol to form MMA by one-step 4.0/). oxidative esterification (Scheme1)[ 6]. In view of energy efficiency and environmental Catalysts 2021, 11, 162. https://doi.org/10.3390/catal11020162 https://www.mdpi.com/journal/catalysts Catalysts 2021, 11, x FOR PEER REVIEW 2 of 16 Catalysts 2021, 11, 162 2 of 16 to MMA [5]. Instead, MAL could also react with methanol to form MMA by one-step ox- idative esterification (Scheme 1) [6]. In view of energy efficiency and environmental cost, cost,the direct the direct oxidative oxidative esterification esterification process process is more is more attractive attractive in comparison in comparison with withthe two- the two-stepstep method. method. However, However, it is it still is still very very challenging challenging for for the the development development of of efficient efficient andand selectiveselective catalyticcatalytic systemssystems underunder moderatemoderate conditionsconditions byby aa one-stepone-step methodmethod [[7,8].7,8]. O 2 H O H 3 C SchemeScheme 1.1. IsobuteneIsobutene oxidationoxidation routesroutes toto produceproduce methylmethyl methacrylatemethacrylate (MMA).(MMA). SupportedSupported gold catalystscatalysts are generallygenerally believed to exhibit good performances in ox- idationidation reactions under under moderate moderate conditions conditions [9–14]. [9–14]. The The special special property property enables enables it to it tobe bea potential a potential candidate candidate to replace to replace traditional traditional Pd-based Pd-based catalysts catalysts in one-step in one-step oxidative oxidative ester- esterificationification [15–22]. [15– Previously,22]. Previously, K. Suzuki K. Suzuki at Asahi at Asahi Kasei Kasei developed developed a SiO a2 SiO–Al2O–Al3–MgO2O3–MgO mul- multipletiple oxides-supported oxides-supported AuNiO AuNiOx catalystx catalyst with with core–shell core–shell st structureructure [15]. [15]. The catalystcatalyst showedshowed goodgood performanceperformance forfor MALMAL toto MMA,MMA, withwith thethe conversionconversion ofof ∼∼60% and selectivity ofof 96–97%.96–97%. After this,this, WangWang etet al.al. observedobserved goodgood activityactivity andand selectivityselectivity over over the the Au/MgO Au/MgO catalyst,catalyst, whichwhich showedshowed conversionconversion ofof 98%98% and selectivity of 99%, respectively [[16].16]. More- over,over, goldgold catalystscatalysts supportedsupported onon differentdifferent transitiontransition metalmetal oxidesoxides andand hydroxyapatitehydroxyapatite havehave beenbeen preparedprepared inin thisthis reactionreaction toto evaluateevaluate thethe catalyticcatalytic performancesperformances [[17–22].17–22]. TheirTheir comparingcomparing resultsresults are are shown shown in in Table Table S1. S1. Based Based on on these these results, results, the the property property of the of supportthe sup- and/orport and/or the particle the particle size ofsize gold of gold has been has been demonstrated demonstrated to be crucialto be crucial for one-step for one-step oxidative oxi- esterificationdative esterification [16,17,21 [16,17,21]. The support]. The withsupport strong with basic strong sites basic and thesites gold and with the agold small with aver- a agesmall particle average size particle are said size to are benefit said theto benefi transformationt the transformation of MAL to of MMA MAL [16 to, 21MMA]. However, [16,21]. althoughHowever, the although activity the and activity selectivity and ofselectivit supportedy of goldsupported catalysts gold exhibited catalysts great exhibited advantages great toadvantages traditional to Pd-based traditional catalysts, Pd-based the catalysts, stability wasthe stability among onewas of among the big one challenges. of the big chal- Recently, layered double hydroxides (HTs) or hydrotalcite-type compounds, which lenges. have a general formula of [M 2+M 3+(OH) ]x+·[(An−) ]·yH O, have attracted great Recently, layered double1 hydroxides−x x (HTs2 ) or hydrotalcite-typx/n 2 e compounds, which interest due to their high surface area, homogeneously dispersed metal atoms and acid– have a general formula of [M1−x2+Mx3+(OH)2]x+·[(An−)x/n]·yH2O, have attracted great interest base properties [23–25]. Up to now, they have been utilized in a wide variety of oxidative due to their high surface area, homogeneously dispersed metal atoms and acid–base prop- reactions, such as the oxidation of benzyl alcohol [26], the oxidative steam reforming erties [23–25]. Up to now, they have been utilized in a wide variety of oxidative reactions, of methanol [27], the styrene epoxidation [28] and, etc. Previously, Zn-Al-mixed oxide- such as the oxidation of benzyl alcohol [26], the oxidative steam reforming of methanol supported gold catalysts were demonstrated by us to display special catalytic performances [27], the styrene epoxidation [28] and, etc. Previously, Zn-Al-mixed oxide-supported gold in selective hydrogenation reactions [29–31]. The interaction between the gold and the catalysts were demonstrated by us to display special catalytic performances in selective support made it a great candidate for the synthesis of gold catalysts with controllable hydrogenation reactions [29–31]. The interaction between the gold and the support made sizes [29,31]. Moreover, the inert activation for the vinyl group enables it a potential it a great
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