固体酸方法降解纤维素

1、 一一. .纤维素降解为葡萄糖纤维素降解为葡萄糖 二二. .葡萄糖降解为葡萄糖降解为HMF HMF 目目 录录Nature,2005,438(10),178Angew. Chem. Int. Ed. 2004, 43, 2955 2958J. AM. CHEM. SOC. 2008,130(38),12787-12793Chem. Mater. 2006, 18, 3039 3045Green Chem., 2008, 10, 10331037Selectivity=90%,yield=40.5%Chem. Commun., 2010, 46, 69356937In addition, the

2、 mesoporous structure also facilitates the transportation of large molecules (such as glucose, cellobiose,cellotriose) in comparison with microporous carbonsAC-N-SO3H-250150 ,24hcelluloseglucoseCov=74.3%, yield=61%celluloseglucoseCov=94.4%, yield=74.5%CMK-3150 ,24hcelluloseglucoseyield=16.7%BC-SO3H/

3、H2O 90Microwave,350W,60minGreen Chem., 2010, 12, 696700ChemSusChem., 2011,4,5558amorphous celluloseFe3O4SBASO3HH2O,150 glucoseGreen Chem., 2010, 12, 15601563Si33C66-823-SO3Hcellulose433K,24h,waterglucoseSel=60.7%,yield=50.4%Yield=50%Chem. Mater. 2009, 21, 186193AC-SO3H亲水性反应，较小表面积2m2/g，固载到SBA-15上有较大的

4、比表面积，催化疏水性反应。比表面积为700-1000m2/g Glucose HMFChem. Commun., 2009, 62766278 |Chem. Commun., 2010, 46, 11151117glucoseIsomerase, borate70,8hfrucoseHCl, water- butanol190,45minHMFyield=63.3%Con=50%,yield=28.2%加入硼酸钠yield=87.8%Green Chem., 2011, 13, 810812celluloseRSO3H ，M(OTf)3, in MeOH,N2 0.5MPa,180,5hmet

5、hyl levulinateYield=75%the first part is the solvolysis of cellulose to sugars, which is mainly catalyzed by PTSA, the second part is the conversion of sugars to methyl levulinate, which is mainly catalyzed by In(OTf)3Solid acid+base酶 + 酸Lewis acid + Brnsted acidGreen Chem., 2011, 13, 109114fructose

6、B(OH)3 NaCl,MIBK: aqueous=4:1150 ,45minHMFcon=92%sel=65%yield=60%glucoseHMFyield=14%150 ,5hChemSusChem 2010, 3, 350 355sel=87.2%, yield=72.3%HMFNMP+CH3SO3- 2h,90fructose HMFGlucoseEMIMCl,100,Cr2+BMIMCl,100,NHC-M,Cr2+DMA-LiBr,Cr2+68%81%80%FructoseGlucoseHMFCr2+, ionic liquid86%H+Green Chem., 2009, 11

7、, 17461749SCIENCE,2007,16,1597-1599ANGEW,2008, 120, 9485 9488ANGEW,2010, 49, 8954 895金属离子金属离子杂多酸杂多酸杂多酸（Heteropoly Acid，简写为HPA ）是由杂原子（如P、Si、Fe、Co等）和多原子（如Mo、W、V、Nb、Ta等）按一定的结构通过氧原子配位桥联组成的一类含氧多酸，具有很高的催化活性，它不但具有酸性，而且具有氧化还原性。 属性为强度均匀的质子酸。Green Chem., 2009, 11, 16271632 heteropolyacid H3PW12O40 as Brnsted

8、acid has the highest acid strength and has higher acidity than H2SO4. Salts of metal cation (Mn+)andPW12O403-(M3/nPW12O40)potentially show Lewis acidityglucose12-MPA,EMIMCl/BMIMClHMFCon=98%，sel=99%Green Chem., 2010, 12, 1253-12623h,393K12-MPA是12-磷钼酸ChemSusChem 2010, 3, 350 355fructoseHMFDMSO,PTA/MIL-101130,30minCon=82%,sel=77%,yield=63%PTA是H3PW12O40, MIL-101金属（铬）有机框架载体J. AM. CHEM. SOC. 2010, 132, 66226623质