DOI: 10.1002/cssc.201300766 Synthesis of 5-Hydroxymethylfurural from Carbohydrates using Large-Pore Mesoporous Tin Phosphate Arghya Dutta, [a] Dinesh Gupta, [b] Astam K. Patra, [a] Basudeb Saha,* [b, c] and Asim Bhaumik* [a] Introduction The discovery of mesoporous materials based on FSM [1] (Folded Sheet Mesoporous) and MCM [2] (Mobil Composition of Matter) in the early 1990s made a breakthrough in the field of materials research not only by solving the pore-size limitation of zeolite chemistry but also because of the introduction of a generalized supramolecular templating approach that gave total control over pore-size tuning. These materials showed pore diameters in the range of 2–4 nm if a cationic surfactant such as cetyltrimethyl ammonium bromide (CTAB) was used as the template. Although the use of different swelling agents can expand the pore dimensions of these materials, [3] the use of block copolymers as structure-directing agents (SDAs) [4] ex- tended the pore size up to 30 nm. Large mesopores are essen- tial for some specific applications such as biomolecule immobi- lization, [5] biocatalysis, [6] protein adsorption and separation, [7] catalytic reactions that involve bulky natural products, [8] etc. In- itially, most research concentrated on MCM-based mesoporous silica materials until Stucky and co-workers proposed a general- ized synthesis route for large-pore mesoporous metal oxides. [9] This opened up the possibility to use rich transition metal chemistry in the vast field of heterogeneous catalysis. Later Tian et al. reported a self-adjusting synthetic process for differ- ent porous transition metal oxides and phosphates with a varie- ty of pore sizes. [10] Among the different types of porous materi- als, metal phosphates are of great importance for their applica- tion in catalysis, [11] ion exchange, [12] conductivity, [13] optoelec- tronics, [14] Li-ion batteries, [15] etc. A low surface area and small pore size are, in general, the main drawbacks of metal phos- phates for their successful utilization in different catalytic reac- tions. As tin phosphates show excellent catalytic [16] and electro- chemical [17] properties, much effort has been devoted to the synthesis of porous tin phosphate materials with high surface areas. [18] However, the large particle size and small pore open- ing of tin phosphate materials remain a problem as they hinder the accessibility of the framework pores for different catalytic processes that involve bulky natural products. Here we report a facile hydrothermal synthesis of large-pore meso- porous aggregated tin phosphate nanoparticles (LPSnP-1) by using Pluronic P123 as the SDA. This material showed a high thermal stability and excellent catalytic activity for the produc- tion of 5-hydroxymethylfurural (HMF) from naturally abundant carbohydrates in an aqueous medium. HMF, one of the top ten bio-based platform chemicals, has received significant atten- tion as it can be used to produce a broad range of chemicals and liquid transportation fuels. [19] As a result of the versatile applications of furfurals, rapid progress in the development of efficient catalytic processes for the conversion of carbohy- drates and biomass has been witnessed over recent years, al- though sustainable and economically viable routes for their production in scalable quantities are yet to be developed. Sev- eral homogeneous Brønsted acidic mineral acids and ionic liq- uids, Lewis acidic metal chlorides and bifunctional Brønsted/ A large-pore mesoporous tin phosphate (LPSnP-1) material has been synthesized hydrothermally by using Pluronic P123 as the structure-directing agent. The material is composed of ag- gregated nanoparticles of 10–15 nm in diameter and has a BET surface area of 216 m 2 g 1 with an average pore diameter of 10.4 nm. This pore diameter is twice as large as that of meso- porous tin phosphate materials synthesized through the sur- factant-templating pathways reported previously. LPSnP- 1 shows excellent catalytic activity for the conversion of fruc- tose, glucose, sucrose, cellobiose, and cellulose to 5-hydroxy- methylfurfural (HMF) in a water/methyl isobutyl ketone bipha- sic solvent to give maximum yields of HMF of 77, 50, 51, 39, and 32 mol %, respectively, under microwave-assisted heating at 423 K. Under comparable reaction conditions, LPSnP-1 gives 12 % more HMF yield than a small-pore mesoporous tin phos- phate catalyst that has an identical framework composition. This confirms the beneficial role of large mesopores and nano- scale particle morphology in catalytic reactions that involve bulky natural carbohydrate molecules. [a] Dr. A. Dutta, Dr. A. K. Patra, Prof. Dr. A. Bhaumik Department of Materials Science Indian Association for the Cultivation of Science 2A & 2B Raja S. C. Mullick Road, Jadavpur, Kolkata 700 032 (India) E-mail : msab@iacs.res.in [b] D. Gupta, Dr. B. Saha Laboratory of Catalysis, Department of Chemistry University of Delhi North Campus, Delhi 110 007 (India) [c] Dr. B. Saha Department of Chemistry, Purdue University 560 Oval Drive, West Lafayette, Indiana 47907 (USA) E-mail : sahab@purdue.edu Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/cssc.201300766.  2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim ChemSusChem 0000, 00, 1 – 10 &1& These are not the final page numbers! ÞÞ CHEMSUSCHEM FULL PAPERS