PROGRAM

DICPSymposium(No.44)onInternationalYoungScientistSymposiumonCatalyticBiomassConversion

(IYCBC)July16‐18,2017

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Welcome Message

It is our great honor to welcome you to attend the DICP Symposium (No.44) on

International Young Scientist Symposium on Catalytic Biomass Conversion (IYCBC),

which will be held in Dalian from 16 to 18 July, 2017.

The aim of this symposium is to promote the research and progress in the area of

biomass conversion, and to create an environment for fruitful discussions and

exchange of ideas on application of catalysts in the sustainable production of value

added chemicals and fuels from biomass, especially for the young scientists from

various countries to make beneficial contact and cooperation.

Dalian has only one international airport, Zhoushuizi Airport, DLC. You can transfer

from Beijing, Shanghai, Guangzhou, Seoul, and Narita airport to Dalian. The

temperature in July in Dalian is around 28 Celsius degree. This is a coastal city and

it feels not like so hot. Bring running shoes if you like to exercise in the seaside.

We are looking forward to your visit and your excellent talk in Dalian.

Contact info

Ms. Xiaochen Zhang

Mobile: +86-15164075730

E-mail: xczhang@dicp.ac.cn

Dr. Huifang Liu

Mobile: +86-18804281227

E-mail: liuhuifang@dicp.ac.cn

Prof. Feng Wang

Mobile: +86-15141146689

E-mail: wangfeng@dicp.ac.cn

1

Program

Conference Hall of Basic Energy Building in DICP

July 16, Sunday

14:00-14:30 Pickup at Hotel

14:30-14:40 Opening Ceremony

Session Chair: Prof. Carsten Sievers/ Prof. Fuwei Li

14:40-15:40 Plenary Lecture: TBD Prof. Tao Zhang Dalian Institute of Chemical Physics, Chinese Academy of Sciences, China

15:40-16:10 Photo taking and coffee break

16:10-16:40 Targeted catalytic upgrading of simplified streams produced from staged biomass degradation Prof. Steven Crossley University of Oklahoma, USA

16:40-17:10 Development of heterogeneous catalysts for hydrogenation of biomass-derived carboxylic acids Prof. Masazumi Tamura Tohoku University, Japan

17:10-17:40 Selective conversion of cellulose into C2–C4 alcohols on solid catalysts Prof. Haichao Liu Peking University, China

18:10- Dinner (invited only)

July 17, Monday

08:00-08:30 Pickup at Hotel

Session Chair: Prof. Haichao Liu/ Prof. Paul Dauenhauer

08:30-09:00 Spectroscopic studies of heterogeneously catalyzed processes for biomass conversion Prof. Carsten Sievers Georgia Institute of Technology, USA

09:00-09:30 Catalytic transformation of cellulose and its derivatives into organic acids Prof. Weiping Deng Xiamen University, China

09:30-10:00 Lignocellulosic fractionation by a tandem organosolv pulping and metal-catalyzed transfer hydrogenolysis Prof. Joseph Samec Stockholm University, Sweden

10:00-10:30 The importance of hydrogen bonds in biomass conversion Prof. Fang Lu Dalian Institute of Chemical Physics, Chinese Academy of Sciences, China

10:30-10:40 Coffee Break

2

10:40-11:10 An integrated, flexible biorefinery process based on formic acid Prof. Ning Yan National University of Singapore, Singapore

11:10-11:40 Molecular-level insights into how the structure of liquid water influences the catalysis of sugar alcohol conversions in aqueous phase heterogeneous catalysis Prof. Rachel B. Getman Clemson University, USA

11:40-12:10 Synthesis of jet fuel range cycloalkanes with lignocellulosic platform compounds Prof. Ning Li Dalian Institute of Chemical Physics, Chinese Academy of Sciences, China

12:10-13:30 Lunch

Session Chair: Prof. Ning Yan/ Prof. Pieter Bruijnincx

13:30-14:00 Strategies for the conversion of biomass to biobased chemicals Prof. Thomas Schwartz University of Maine, USA

14:00-14:30 Catalytic conversion of biomass to fine chemicals and fuels Prof. Yanqin Wang East China University of Science and Technology, China

14:30-15:00 Oxidative chemistries for levulinic acid conversion: finding opportunities for biomass in an age of inexpensive hydrocarbons Prof. Jesse Bond Syracuse University, USA

15:00-15:30 Hydrogenation of 5-HMF through Homogeneous Catalysis Dr. Zhanwei Xu Dalian Institute of Chemical Physics, Chinese Academy of Sciences, China

15:30-15:40 Coffee Break

15:40-16:10 Platform molecules from the carbohydrate and lignin fractions of lignocellulosic biomass: on advanced feed characterization and catalyst development Prof. Pieter Bruijnincx Utrecht University, Netherlands

16:10-16:40 Catalytic conversion of lignin to aromatic hydrocarbons Prof. Chen Zhao East China Normal University, China

16:40-17:10 Renewable bubbles, bottles and (rubber) bands from biomass Prof. Paul Dauenhauer University of Minnesota, USA

17:10-17:40 Converting of lignin into aromatics by tungsten carbide Prof. Changzhi Li Dalian Institute of Chemical Physics, Chinese Academy of Sciences, China

17:40- Dinner

July 18, Tuesday

08:00-08:30 Pickup at Hotel

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Session Chair: Prof. Yanqin Wang/ Prof. Joseph Samec

08:30-09:00 Strong metal-support interaction or “overcoat” enabled catalysts for efficient transformation of biomolecules Prof. Fuwei Li Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, China

09:00-09:30 The importance of puckering in carbohydrate conversion: It’s elementary Prof. Heather Mayes University of Michigan, USA

09:30-10:00 Catalytic conversion of lignin models and extracts into oxygenates Prof. Feng Wang Dalian Institute of Chemical Physics, Chinese Academy of Sciences, China

10:00-10:10 Coffee Break

10:10-12:00 Discussions (Prof. Feng Wang/ Prof. Carsten Sievers)

12:00-13:00 Lunch

13:00-17:00 Lab visit

17:00 End of the symposium and departure

4

Targeted catalytic upgrading of simplified streams produced from staged biomass degradation

Steven Crossley Chemical, Biological and Materials Engineering, University of Oklahoma, USA

stevencrossley@ou.edu

Abstract: The carbon efficient conversion of biomass to renewable fuels and chemicals is

plagued by highly inefficient processes. Thermal degradation of biomass yields a stream with several chemically incompatible compounds that polymerize upon storage. Here we discuss the benefits of a multistage upgrading approach, where specific catalytic strategies may be implemented to target specific chemistries that increase yields to valuable products per mass of biomass. We discuss the tradeoffs between the increased process complexity and yields to useful products, and highlight the new chemistries that can be employed with such an approach. We highlight the role of abundant and problematic carboxylic acids, and the coupling reactions that can occur in these purified streams, including ketonization and selective acylation reactions. The kinetics and mechanism of these reactions will be presented, and the resulting influence of these reactions on life cycle emissions resulting from the production of fuels and chemicals from biomass. Bio:

Steven Crossley received his Ph.D. in chemical engineering with Daniel Resasco from the University of Oklahoma in 2009. From 2009-2011, he conducted research at ConocoPhillips, now Phillips 66, in the areas of fluid catalytic cracking and hydrocracking. In August 2011, Dr. Crossley joined the University of Oklahoma as an assistant professor. His research focuses on reaction kinetics and nanomaterials synthesis. Most of his students’ projects involve kinetic fitting and evaluation of reaction mechanisms relevant to biomass conversion over zeolites or metals supported on reducible oxides. He is also a

member of the Center for Interfacial Reaction Engineering, where his group studies heterogeneously catalyzed reactions in biphasic systems. Dr. Crossley is the recipient of the ACS PRF DNI award (2014) and the NSF CAREER award (2017). He has chaired and co-chaired numerous sessions in AIChE and ACS national meetings. He has published over 30 peer reviewed journal articles, including high impact journals such as Science and Energy and Environmental Science, and given over 40 oral presentations at national meetings and departmental seminars.

5

Development of heterogeneous catalysts for hydrogenation of biomass-derived carboxylic acids

Masazumi Tamura Department of Applied Chemistry, School of Engineering, Tohoku University, Japan

mtamura@erec.che.tohoku.ac.jp Abstract:

Carboxylic acids are one of biomass-derived chemicals, and hydrogenation of carboxylic acids can produce valuable alcohols, which are important intermediates for organic synthesis, lubricants, surfactants, plasticizers, cosmetics and biofuels. Hydrogenation of carboxylic acids is generally difficult because of lower reactivity of the carboxyl group, therefore, development of effective heterogeneous catalysts has been required. Recently, we have developed heterogeneous metal oxide modified (noble) metal (M+MOx) catalysts, and demonstrated that these catalysts are effective for hydrogenation of various carboxylic acids to the corresponding alcohols. In this presentation, I will introduce the details of these catalyst systems, and an overview of some recent efforts from our lab will be presented. Bio:

Masazumi Tamura earned a Bachelor’s degree in Chemistry in 2003 from Kyoto University. He then received the Master’s degree of Engineering from University of Tokyo in 2005 and the PhD degree of Engineering from Nagoya University in 2012. From 2005, he was a researcher at Material Research Laboratories in Kao Corporation. From 2012 till now, he works as an assistant professor at Department of Applied Chemistry in Tohoku University. Masazumi Tamura got the Research Award in Aoba Foundation for the Promotion of Engineering (2015) and the Catalysis Society of Japan Award for Young Researchers (2017). He also won the 31th Young

Scholar Lectures of Chemical Society of Japan in 2017.

6

Selective conversion of cellulose into C2–C4 alcohols on solid catalysts

Haichao Liu Beijing National Laboratory for Molecular Sciences, College of Chemistry and

Molecular Engineering, Peking University, China hcliu@pku.edu.cn

Abstract:

Cellulose is the most abundant source of biomass on earth. Its selective conversion into alcohols (including polyhydric and mono- alcohols) provides a viable route toward the sustainable synthesis of fuels and chemicals from biomass. In this work, we report our progress in catalytic conversion of cellulose into C2-C4 alcohols, ethylene glycol, propylene glycol and especially C4 alcohols, on WO3-based catalysts, including the understanding on the structural requirements and reaction mechanism.

This work was carried out mainly by Drs. Y. Liu, C. Chao and T. Deng under the financial supports from the National Natural Science Foundation of China and National Basic Research Project of China. Bio:

Haichao Liu received his B.S. and M.S. degrees from Sichuan University in 1990 and 1993, respectively, and Ph.D degree from Research Institute of Petroleum Processing in 1996. From 1997 to 2003, he did postdoctoral research at The University of Tokyo and The University of California at Berkeley. At the end of 2013, he joined the faculty of Peking University where he is now Changjiang Distinguished Professor of Chemistry. He is an editor of Journal of Catalysis and associate editor of Chinese Journal of Catalysis. His research interests currently focus on molecular catalysis and

sustainable energy chemistry with emphasis on design of heterogeneous catalysts and control of reaction pathways for selective conversion of biomass and its derivatives to important chemicals.

7

Spectroscopic Studies of Heterogeneously Catalyzed Processes for Biomass Conversion

Carsten Sievers School of Chemical & Biomolecular Engineering, Georgia Institute of Technology, USA

carsten.sievers@chbe.gatech.edu Abstract:

The conversion of biomass to value-added chemicals and fuels is one of the great challenges in modern chemical engineering. Since biomass contains much more oxygen than most chemicals and fuels, it is critical to develop processes for removing oxygen containing functional groups. Catalysts will play a critical role in most of these processes because they are critical for providing the required selectivity to certain products. Specific reactions for oxygen removal include hydrodeoxygenation (HDO), dehydration, condensation, and ketonization. The development of efficient catalysts for these reactions will require a good understanding of the interactions of biomass-derived oxygenates with potential catalysts. Our work aims to provide this insight using in-situ spectroscopy.

Selective dehydration can be used to produce specific chemicals from biorenewable feedstocks. In this talk, dehydration of glycerol over niobia catalysts with different concentrations of Brønsted and Lewis acid sites will be described. Important surface species are identified by in-situ IR spectroscopy, and it is shown how different acid sites affect different dehydration paths and the formation of coke. In a separate study, we use time-resolved operando IR spectroscopy to elucidate the reaction paths of aromatic oxygenates during HDO over H-BEA and Pt/H-BEA zeolites. Trends in reactivity and selectivity are explained based on nature of surface species formed from different oxygenates. It is also shown that carbonaceous deposits can undergo several stages of aging before significant deactivation is observed. Most importantly, oxygenates with two functional groups can form strongly bound surface species that prevent diffusion of reactants and products. The new insight will allow for developing protocols for efficient regeneration of spent HDO catalysts. Bio:

Carsten Sievers obtained his Diplom and Dr. rer nat. degrees in Technical Chemistry at the Technical University of Munich, Germany. Under the guidance of Prof. Johannes A. Lercher, he worked on heterogeneous catalysts for various processes in petroleum refining including hydrogenation of aromatics in Diesel fuel, alkylation, alkane activation, and catalytic cracking. Additional research projects included novel catalytic system, such as supported ionic liquids. In 2007, he moved to the Georgia Institute of Technology to work with Profs. Christopher W. Jones and Pradeep K. Agrawal as a postdoctoral fellow. His primary focus was the development of catalytic processes for biomass depolymerization and

synthesis of biofuels. He joined the faculty at the Georgia Institute of Technology in 2009. His research group is developing catalytic processes for the sustainable production of fuels and chemicals. Specific foci are on the stability and reactivity of solid catalysts in aqueous phase, surface chemistry of oxygenates in water, production of specific chemicals from biomass, applied spectroscopy, synthesis of well-defined catalysts, methane conversion, mechanocatalysis, CO2 capture, pyrolysis, and gasification. He is Director of the Southeastern Catalysis Society, Director of the ACS Division of Catalysis Science & Technology and the AIChE Division of Catalysis and Reaction Engineering, and Editor of Applied Catalysis A: General.

8

Catalytic transformation of cellulose and its derivatives into organic acids

Weiping Deng College of Chemistry and Chemical Engineering, Xiamen University, China

dengwp@xmu.edu.cn Abstract:

The catalytic transformation of cellulose into value-added organic acids such as lactic acid and adipic acid, is one of the most promising routes for biomass utilization. Such transformation follows the structural feature of cellulose, and retains the majority of elements such as carbon and oxygen, thus agreeing well with the principle of high atomic economy. Herein, we have demonstrated that a simple cation system (e.g. PbII) could enable the efficient transformation of cellulose and even unpurified biomass into lactic acid. We also identified the key steps for the formation of lactic acid. However, the application of this system is limited by the toxicity of PbII. In this context, we developed an AlIII-SnII-based dual cation system, which was more effective and environmental benign for the synthesis of lactic acid. AllII is responsible for the isomerization, while SnII mainly catalyzes the retro-aldol fragmentation. The combination of the two cations makes the system work multi-functionally and efficiently for cellulose conversion. In addition, we have developed a Pt-based catalytic system for the synthesis of adipic acid by de-hydroxylation of glucaric acid, which can be obtained from selective oxidation of glucose. In the system, acetic acid ad a small amount of halogen were introduced to assist the activation of OH group, and then the Pt catalyst catalyzed the cleavage of C–O bond, giving rise to the adipic acid. The system has been applicable in other OH removal reactions. Bio:

Dr. Deng obtained his Ph.D. degree from Xiamen University in 2009. Afterwards, he joined the same university as an engineer in the National Engineering Laboratory for Green Chemical Productions of Alcohols, Ethers and Esters. In 2014, he moved to College of Chemistry and Chemical Engineering as an assistant professor. Dr. Deng received the Young Scientist Award presented by International Association of Catalysis Societies in 2008 and 2012, respectively. In 2012, he received the Catalysis Raising Star Award, which was presented by the Catalysis Society of China, because of his

outstanding work on catalytic conversion of cellulose. His research focuses on biomass transformation catalysis, mainly including (1) new strategy for the catalytic conversion of cellulose; (2) new catalytic materials for lignin valorization; (3) catalysis for transformation of bio-based platform chemicals. He has published about 40 peer-reviewed papers in international journals including Nat. Commun., Chem. Commun., ACS Catalysis, J. Catal., Green Chem., ChemSusChem, etc.

9

Lignocellulosic fractionation by a tandem organosolv pulping and metal-catalyzed transfer hydrogenolysis

Joseph Samec Department of Organic Chemistry, Stockholm University, Sweden

joseph.samec@su.se

Abstract: Current processes for the fractionation of lignocellulosic biomass focus on the

production of high-quality cellulosic fibers for paper, board, and viscose production. The other fractions that constitute a major part of the lignocellulose are treated as waste or used for energy production. The transformation of lignocellulose beyond paper pulp to commodity and fine chemicals, polymer precursors, and fuels is the only feasible alternative to current refining of fossil fuels as a carbon feedstock. Inspired by this challenge, scientists and engineers have developed a plethora of methods for the valorization of biomass. However, most studies have focused on using one single purified component from lignocellulose that is not currently generated by the existing biomass fractionation processes. A lot of effort has been made to develop efficient methods for lignin depolymerization. The step to take this fundamental research to industrial applications is still a major challenge.

This talk will present an alternative approach, in which the lignin valorization is performed in concert with the pulping process. This enables the fractionation of all components of the lignocellulosic biomass into valorizable streams. Lignocellulose fractions obtained this way (lignin oil, glucose, etc.) can be utilized in a number of existing procedures. Bio:

Joseph Samec received his Ph.D. from University of Stockholm in 2005 with Prof. Bäckvall as supervisor. During his PhD he visited Prof. Casey at UW, Madison for 4 months. After a postdoctoral training with Prof. Grubbs at CalTech during 2006-2007, he was appointed as Assistant Professor at University of Uppsala in Sweden. In 2015 he joined the faculty at Stockholm University where he is currently professor. His research interest focuses on green chemistry in organic synthesis and biomass processing and applications. 2012 he founded RenFuel, a start-up company that is producing

biofuels from lignin and in 2017 he founded RenCom that produces materials from lignin.

10

The importance of hydrogen bonds in biomass conversion

Fang Lu Dalian Institute of Chemical Physics, Chinese Academy of Sciences, China

lufang@dicp.ac.cn Abstract:

Hydrogen bonding is one of the most important and widely existed forms of molecular bonding interaction in nature. It plays a vital role in assembling the structure of protein, polymers and biomass compounds. Numerous hydrogen bonds formed by the hydroxyl groups within the biomass, resulted in totally different chemical structure with fossil resourced chemicals. The strong hydrogen bonding networks make the highly ordered and crystallized structures in plants which seriously impede the efficient utilization of biomass. Therefore, precise recognition, comparison and better understanding H-bonds in biomass will pave an efficient way to convert biomass into valuable chemicals and liquid fuels.

In our previous work, we demonstrated for the first time that the linear correlation between the natural logarithm of OH proton chemical shifts (ln δ) and inverse of NMR operating temperature (1/T) for sugar derived alcohols. The slopes (A) of the plot could provide the information on H-bonding vibration energy difference of intra- or intermolecular H-bonds in hydroxyl groups. Intramolecular H-bonds show small slope values and small H-bonding vibration energy difference. Consequently, the reactivity of the intramolecularly hydrogen-bonded hydroxyl group is more active than that of the intermolecular one during the nucleophilic etherification reaction.

In the present work, we report a synthetic route to diethyl terephthalate (DET), using trans,trans-muconic acid (TTMA), ethanol, and ethylene as the reactants, through a cascade process combining esterification, Diels–Alder cycloaddition, and dehydrogenation. The key esterification reaction changes the inter- and intra-molecular hydrogen bond of TTMA, and improves the solubility of the reaction products in ethanol. Meanwhile, the electronic properties of esterification products are different with TTMA which promoting the Diels–Alder reaction with ethylene. With silicotungstic acid as the catalyst, nearly 100% conversion of muconic acid was achieved, and the cycloadducts were formed with more than 99.0% selectivity. The total yield of diethyl terephthalate reached 80.6% based on the amount of muconic acid used in the two-step synthetic process. Bio:

Professor Fang Lu is currently a professor of Dalian Institute of Chemical Physics (DICP). Her research interests focus on designing new catalytic materials, developing new methodologies for catalytic dehydration and hydrogenation of biomass materials. She presided over the completion of many foundations, such as National Natural Science Foundation of China, international cooperation with BP and Haldor Topsoe. Prof. Lu has published 30 research papers and 1 scientific book, and applied 38 patents for invention.

11

An Integrated, Flexible Biorefinery Process Based on Formic Acid

Ning Yan Department of Chemical & Biomolecular Engineering, National University of

Singapore, Singapore ning.yan@nus.edu.sg

Abstract:

We communicate a new process for the fractionation and upgrading of woody biomass using formic acid as reaction media. Based on the selection of treatment time and temperature, hemicellulose and lignin, in term, could be separated from cellulose in wood in the presence of pure or diluted formic acid. The hemicellulose is extracted in the form of depolymerized sugars ready for direct further use, while the extracted lignin maintains a high reactivity for making aromatic compounds. The crystallinity and molecular weight of cellulose, depending on the application purpose, can be controlled by processing temperature and formic acid concentration. Being the simplest carboxylic acid, formic acid is sufficiently stronger (pKa = 3.75, 20 °C) than carboxylic acids with longer chains (e.g., pKa(acetic acid) = 4.76, 25 °C). Compared with H2SO4—the most extensively used mineral acid for biomass treatment—formic acid evaporates without leaving any residue, benefitting the post-reaction process. Furthermore, formic acid is an excellent hydrogen donor for hydrogenation and hydrodeoxygenation reactions. This feature enables process integration when combined with a metal catalyst. We demonstrate the power of such a combination by converting cellulose directly to a value-added product, 2,5-hexanedione (HDN), in up to 40% yield in a one-pot manner. Formic acid played as the solvent, the depolymerization/dehydration catalyst and the hydrogen donor reagent. Moreover, we have demonstrated the similar system to be applicable to the liquefaction of chitin, the second most abundant polymer after cellulose. Bio:

Ning Yan obtained his bachelor and PhD degrees from Peking University in 2004 and 2009, respectively. Thereafter, he worked as a Marie-Curie Research Fellow with Prof. Paul Dyson at Ecole Polytechnique Federale de Lausanne (EPFL), Switzerland. He joined the National Universityof Singapore (NUS) as an Assistant Professor and established the Lab of Green Catalysis in 2012. His research interests include green chemistry, biomass conversion and catalysis. Recently, he won the NUS Young Investigator Award, the G2C2 Young Researcher Award and the Environment, Sustainability and

Energy Early Career Award from Royal Society of Chemistry.

12

Molecular-Level Insights into How the Structure of Liquid Water Influences the Catalysis of Sugar Alcohol Conversions in Aqueous Phase Heterogeneous Catalysis

Rachel B. Getman Department of Chemical and Biomolecular Engineering, Clemson University

rgetman@clemson.edu

Abstract: Multiple applications in renewable energy, including direct fuel cells and biomass

reforming, rely on aqueous phase heterogeneously-catalyzed reactions. Often, these applications use expensive transition metal catalysts, such as platinum or platinum alloys. A goal of our work is to understand the molecular-level ways in which these catalysts function, so that we may design less expensive catalysts for these (and other) applications. Experiments and simulations have uncovered a variety of ways in which water influences surface phenomena in aqueous phase heterogeneous catalysis. For example, it alters reaction intermediate and transition state energies, co-catalyzes certain reaction steps, and controls which catalytic pathways are followed. However, the full range of ways in which H2O molecules influence catalytic behavior, including how they influence catalytic thermodynamic and kinetic quantities, remains to be uncovered. In this work, we use a combination of density functional theory (DFT) and classical molecular dynamics (cMD) to examine how the structure of liquid water at the catalyst interface influences Pt-catalyzed sugar alcohol conversions, which are important in biomass upgrading and direct methanol fuel cells. Specifically, we show how the structure of liquid water influences the thermodynamics of catalytic surface intermediates and transition states and the frequency factors and activation barriers of catalytic reactions. We show that hydrogen bonding between liquid water and catalytic species influences these quantities significantly and make general hypotheses about how catalytic mechanisms play out in aqueous phase. Bio:

Rachel B. Getman is presently an Assistant Professor of Chemical and Biomolecular Engineering at Clemson University; however, her tenure and promotion package was recently approved, and she will be an Associate Professor starting in August 2017. She is the first woman to be tenured and promoted in Clemson University’s Department of Chemical and Biomolecular Engineering in its 100-year history. Dr. Getman’s research group uses quantum chemical calculations and Monte Carlo and molecular dynamics simulations to investigate molecular-level phenomena at fluid/solid interfaces. She is particularly interested in catalytic processes that occur under aqueous

conditions and in catalysis involving metal-organic frameworks (MOFs). Dr. Getman holds a CAREER award from the National Science Foundation studying how the structure of liquid water influences the free energies of catalytic surface intermediates at water/metal catalyst interfaces.

Dr. Getman earned her PhD from the University of Notre Dame in 2009, where she worked with Prof. William F. Schneider studying catalytic oxidations under realistic reaction conditions. From 2009 – 2011, she was a Postdoctoral Research Fellow with Prof. Randall Q. Snurr at Northwestern University, studying gas storage in MOFs. Dr. Getman started her independent career in August 2011, just three months after the birth of her first child, a daughter.

13

Synthesis of jet fuel range cycloalkanes with lignocellulosic platform compounds

Ning Li Dalian Institute of Chemical Physics, Chinese Academy of Sciences (CAS), China

lining@dicp.ac.cn

Abstract: In recent years, the synthesis of jet fuel range hydrocarbons with the lignocellulosic

platform compounds has drawn a lot of attention. So far, most of the reported work about the lignocellulosic bio-jet fuel is concentrated on the production of C8-C16 chain alkanes. Compared with conventional jet fuels (mixtures of chain alkanes and cyclic hydrocarbons), these alkanes have lower densities (or volumetric heat values). In real application, they must be blended with conventional jet fuel to meet the specification of aviation fuels. As a solution to this problem, it is still necessary to develop some new synthetic routes for jet fuel range cycloalkanes. Cyclopentanone and cyclopentanol are two chemicals which can be selectively produced by the aqueous-phase hydrogenation of furfural. In this work, a series of jet fuel range cycloalkanes were selectively produced by the C–C coupling reactions (such as hydroxylalkylation/alkylation, aldol condensation, Guerbet reaction, etc.) of cyclopentaone or cyclopentanol followed by the hydrodeoxygenation or hydrogenation. As an extension of this work, we also developed some new routes for the synthesis of jet fuel range cycloalkanes with acetone and its self-condensation products (mesityl oxide, methyl isobutyl ketone (MIBK) and diacetone alcohol). The cycloalkanes obtained in this work have higher densities. As a potential application, they can be used as additive to improve the volumetric heat values of conventional bio-jet fuel. Bio:

Ning Li got his Bachelor and Master degree in Jilin University in 1997 and 2000. In 2004, he was awarded Ph. D degree by Dalian Institute of Chemical Physics, Chinese Academy of Sciences. From 2005 to 2008, he worked as post-doc in Institute of Research on Catalysis Lyon (IRCE LYON) under the financial support of CNRS post-doctoral fellowship and Marie Curie (FP-6) international incoming fellowship from European Commission. Then he joined the research group of Prof. George W. Huber in Department of Chemical Engineering of University of Massachusetts- Amherst and

worked there for two years on the hydrodeoxygenation of biomass derived oxygenates to high octane number bio-gasoline. In September 2009, he returned to China and joined Dalian Institute of Chemical Physics as a candidate of 100-talent program. Currently, his research interest mainly concentrated on the synthesis of jet fuel range hydrocarbons with lignocellulosic platform compounds.

14

Strategies for the Conversion of Biomass to Biobased Chemicals

Thomas J. Schwartz Department of Chemical & Biological Engineering, University of Maine, USA

thomas.schwartz@maine.edu Abstract:

The prevalence of “light” (C1-C3) hydrocarbons obtained from shale gas motivates a need to find alternative sources of higher-carbon-number molecules suitable for producing commodity and specialty chemicals. Biomass is attractive in this regard because it is composed of monomers with five or more carbons, and it natively contains the oxygenated functionality that is common to high-value chemicals. However, with a carbon-to-oxygen ratio near unity, selective de-functionalization of biomass is a key challenge for producing biobased chemicals. One attractive strategy for obtaining value-added chemicals from biomass uses a combination of chemical and biological catalysis, whereby biological catalysts are used to produce selectively-functionalized platform molecules that are subsequently upgraded using heterogeneous chemical catalysts. We will present an analysis that compares the moieties that can be accessed by biological catalysis with the conversions that are available using heterogeneous chemical catalysis. Based on this analysis we suggest that biologically-derived platform molecules possessing three distinct functional groups provide the most flexibility for subsequent catalytic upgrading, and we extend this analysis to explain reactivity trends using chemically-derived platform molecules as well.

Such reactions require carefully-designed active sites. In an example of this requirement, we show that 5-hydroxymethylfurfural (HMF) can be selectively functionalized using acidic zeolite catalysts, thereby allowing for the production of a series of homologous monomers that can be upgraded to novel thermoplastic polymers. In particular, our results are suggestive of a strong influence of catalyst morphology on both activity and selectivity during the etherification of HMF with ethanol, butanol, cyclohexanol, and phenol.

Bio:

Thomas J. Schwartz received his Bachelors of Science degrees in Chemical Engineering and Biological Engineering from the University of Maine in 2010. While a student at UMaine, he helped develop a process known as “Thermal Deoxygenation,” a patented, non-catalytic means of producing drop-in hydrocarbon fuels from biomass. Upon graduation from UMaine, he moved to the University of Wisconsin to pursue a Ph.D. in Chemical Engineering under the supervision of Prof. James Dumesic. There, as an NSF Graduate Research Fellow, he undertook research in heterogeneous catalysis and reaction kinetics, with projects focusing on the design of

catalytically active sites that can be used for the production of biobased chemicals using combinations of chemical and biological catalysis. In 2015, Dr. Schwartz joined the faculty of the Department of Chemical and Biological Engineering at the University of Maine, where he is also affiliated with the Forest Bioproducts Research Institute (FBRI) and the Laboratory for Surface Science and Technology (LASST). His research group seeks to develop a molecular-level understanding of processes that occur on catalytic surfaces used for the conversion of carbon-based feedstocks to chemicals and fuels. Current research projects focus on the conversion of biomass to novel monomers and the hydrogenolysis of C-Cl and C-O bonds. He is active in the ACS Division of Catalysis Science & Technology as well as the AIChE Division of Catalysis and Reaction Engineering.

15

Catalytic conversion of biomass to fine chemicals and fuels

Yanqin Wang Shanghai Key Laboratory of Functional Materials Chemistry and Research Institute

of Industrial Catalysis, East China University of Science and Technology, China wangyanqin@ecust.edu.cn

Abstract:

Being the only sustainable source of organic carbon, biomass is playing an ever-increasingly important role in our energy landscape. Plant-derived lignocellulosic biomass is considered as an important alternative source to fossil reserves for the production of chemicals and fuels, but the inertness and complexity of lignocellulose makes its depolymerization and usage difficult. Cellulose, as the main component of lignocellulose, can be converted to 5-hydroxymethylfurfural (HMF), one of the most versatile and important building blocks, because it can be upgraded into a large number of chemicals and fuels, such as 2,5-furandicarboxylic acid (FDCA), 2,5-dimethylfuran (DMF) and long-chain alkanes, while its selective conversion to HMF is still a challenge. Lignin, as the most energy-dense fraction of biomass and containing valuable aromatic functionalities, is the only one large-volume renewable source of aromatic chemicals, but its depolymerization and following hydrodeoxygenation to aromatics hydrocarbons is also challenging. To solve these problems, we designed various catalysts to convert cellulose into HMF, lignin to aromatic hydrocarbons and even raw woody biomass to alkanes separately or in full utilization. Bio：

Prof. Yanqin Wang is the full professor at East China University of Science and Technology. Yanqin Wang studied Chemistry at Shandong University and finished her Doctorate degree at Peking University. After this, she worked as Postdocs at Bar-Ilan University (Israel), Max-Planck Institute of Colloid and Interface Science (Germany) and Max-Planck Institute of Coal Research (Germany). In 2004, she joined East China University of Science and Technology, China, as a full professor. Her research interests are nano/porous materials and catalysis, mainly focusing on the research areas below: (1)

Hydrodeoxygenation of biomass and biomass related compounds (2) Dehydration/hydration, hydrogenation and oxidation of biomass-derived compounds (3) Micro/mesoporour materials synthesis and catalytic properties (4) Nanomaterials synthesis and catalytic properties.

16

Oxidative Chemistries for Levulinic Acid Conversion: Finding Opportunities for Biomass in an Age of Inexpensive Hydrocarbons

Jesse Q. Bond Department of Biomedical and Chemical Engineering, Syracuse University, USA

jqbond@syr.edu

Abstract: Levulinic acid (LA) is an interesting bio-based chemical. Its synthesis from various

lignocellulosic sugars is relatively straightforward, and its multifunctional nature opens the door to numerous downstream processing options. Unfortunately, commercial development of levulinic acid has never truly materialized. In part, this may be attributed to the fact that, despite its promise, levulinic acid upgrading has not yet allowed economically viable production of large-market commodities—e.g., levulinic acid based fuels are too expensive to compete, at present, with petroleum derivatives. In contrast, synthesis of oxygenated hydrocarbons is relatively challenging from crude oil and natural gas, and biomass may, at times, be able to provide a competitive advantage. As an example, we consider aerobic, oxidative cleavage of levulinic acid, which produces maleic anhydride (MA) in good yield. The strategy is interesting in that it connects lignocellulose, via levulinic acid, with the existing maleic anhydride market, which is robust and relatively high-value.

Oxidative cleavage of LA occurs over supported vanadates, and we have demonstrated single-pass MA yields as high as 71% of the theoretical maximum at 573K. The underlying chemistry is intriguing: oxidative ketone cleavage over supported vanadium oxides will, in general, break C–C bonds positioned internally to the ketone group, yet formation of maleic anhydride (C4) from levulinic acid (C5) requires cleavage of the terminal C–C bond. We demonstrate that monofunctional ketones, such as 2-pentanone, will preferentially cleave at internal positions; thus, this unanticipated selectivity is unique to bifunctional LA. To elucidate the mechanistic source of this disparity, we examine trends in oxidative cleavage rate and oxidative cleavage selectivity with variation in catalyst makeup and ketone structure. Bio：

Jesse Bond received his B.S. in Chemical Engineering from Louisiana State University, where he developed an interest in catalysis and reaction engineering. His PhD and Postdoctoral training were under the guidance of Thatcher Root and Jim Dumesic in the Department of Chemical and Biological Engineering at the University of Wisconsin, Madison. In 2011, he joined the faculty of Syracuse University as an Assistant Professor in the Department of Biomedical and Chemical Engineering. His research group focuses on developing and understanding catalytic technologies for upgrading abundant

natural resources.

17

Hydrogenation of 5-HMF through Homogeneous Catalysis

Zhanwei Xu Dalian Institute of Chemical Physics, Dalian National Laboratory for Clean Energy

(DNL), China xuzhanweidut@163.com

Abstract:

5-HMF, a versatile platform from glucose, was converted to chemicals through homogeneous Ru or Ir complex. Ru-catalyzed reductive amination of 5-HMF with amines produced functional amines which might be used for preparing pharmaceuticals or polymers. We report the synthesis of bis(hydroxylmethylfurfuryl) -amine (BHMFA) by reacting 5-HMF with primary amines in the presence of homogeneous RuII catalysts having sterically strained ligands. A range of primary amines, such as aliphatic and benzyl amines, are readily converted with 5-HMF to form the corresponding BHMFA in good yields.

Selective hydrogenation of HMF in aqueous solution by Cp*Ir complex bearing OH group generated ketones with a super high activity. Diketones are ubiquitous blocks for organic synthesis. A bipyridine ligand with both dimethylamino and ortho-hydroxyl groups achieved a turnover frequency (TOF) of 31560 h−1 by H2 and a TOF of 6140 h−1 by formic acid. Bio:

Zhanwei Xu, received his PhD degree in Dalian University of Technology majoring in Organic Chemistry in 2013. He moved to DICP as a postdoctor majoring in biomass conversion supervised by Professor Z. Conrad Zhang. He was an associated professor in DICP from 2016. His interests include 5-HMF production, catalytic transformation of bio based furans, e.g., 5-HMF and furfural.

18

Platform molecules from the carbohydrate and lignin fractions of lignocellulosic biomass: on advanced feed characterization and catalyst development

Pieter Bruijnincx Inorganic Chemistry and Catalysis, Utrecht University, Netherlands

P.C.A.Bruijnincx@uu.nl Abstract:

An overview of some recent efforts from our lab will be presented, focusing on the catalytic valorization of the primary components of lignocellulosic biomass and the further conversion of renewable platform molecules to either new or drop-in chemicals. Two routes to renewable aromatics will be highlighted, i.e. by tandem catalytic lignin depolymerization and from biobased furanics via a modified Diels-Alder aromatization route, as well as our work on the Lebedev ethanol-to-butadiene reaction. As the complex structural nature of the biomass feed, lignin in particular, requires the development of new catalytic conversion strategies to go hand in hand with advanced structural characterization, recent new insights into the structure of (technical) lignins and humins will also be presented. Bio:

Pieter Bruijnincx obtained his Ph.D. (2007) degree in Chemistry from Utrecht University with the highest distinction with his doctoral studies focusing on the development of new, bioinspired homogeneous catalysts for selective oxidation reactions. After a postdoctoral fellowship at the University of Warwick (UK) on catalytic anticancer drugs, he returned to Utrecht in 2009 to take up a tenure track Assistant Professor position at the Inorganic Chemistry & Catalysis group. He is now a tenured Associate Professor Catalysis for Renewables and his research focuses on new conversion routes and

the design of new catalyst materials for the sustainable production of new and drop-in chemical building blocks, mainly from biomass. Recent examples of research topics include the catalytic depolymerization of lignin and humins and further catalytic upgrading of lignin-derived aromatics, the conversion of ethanol to butadiene, a novel route for furanics-based aromatics production, fatty acid isomerization, and catalyst development for levulinic acid hydrogenation. In addition to catalyst design and (in situ) catalyst characterization, particular emphasis is put on advanced structural characterization of the complex biomass feeds and waste streams (e.g. industrial lignins and humins). In addition to his biomass valorization research, he also works on the development of new catalytic concepts at the interface of homogeneous and heterogeneous catalysis, e.g. Pickering Emulsions for catalysis or Single Atom Catalysts. Bruijnincx has co-authored >85 papers (h index 28, total citations >4200). He is a member of the editorial advisory board of ChemSusChem and was elected member of the De Jonge Akademie (Young Academy) of the Royal Netherlands Academy of Arts and Sciences in 2015.

19

Catalytic Conversion of Lignin to Aromatic Hydrocarbons

Chen Zhao Shanghai Key Laboratory of Green Chemistry and Chemical Processes, School of Chemistry and Molecular Engineering, East China Normal University, Shanghai,

China czhao@chem.ecnu.edu.cn

Abstract:

Lignin, the second abundant lignocellulose resource, is rich in aromatic rings and energy density that make it attractive as a promising renewable bio-resource to generate fuels and chemicals. However, the complexity of its three-dimensional cross-linking polymeric structure leads to its low solubility in conventional organic solvents, as well as small collision possibility of C-O-C linkage with active catalytic sites. Herein, we provide two approaches for producing aromatic hydrocarbons from lignin. The first route is that lignin is directly hydrodeoxygenated to cycloalkanes, then such formed alkane mixtures are dehydrogenated to aromatic hydrocarbons and hydrogen over Ni based catalysts in a one-pot process. It should be noted that the important chemical of ethyl-benzene can be manipulated to be generated from the majority of C8 cycloalkanes. Meanwhile, the co-produced hydrogen can be used for efficient biomass HDO in an integrated process, such as HDO of lipids to kerosene-ranged hydrocarbon. The second route is based on novel routes that are able to one-pot selective hydrodeoxygenation of lignin derived aryl ether mixture to C6-C9 aromatic hydrocarbons over Ru based on in aqueous phase. We believe that the developed highly integrated new and efficient lignin transformation system can provide intrinsic insights for direct liquefaction of the abundant cellulolytic enzyme lignin, as well as inspiring thoughts in exploiting waste lignocellulose and sulfated/alkali lignin to produce value-added aromatics. Bio:

Dr. Chen Zhao received her doctorate (Ph.D.) in the Chemistry Department of Peking University, China, in 2009. She performed her postdoctoral work in the Chemistry Department of TU München for one year. From 2010 to 2013, she worked as a senior scientist and group leader in the same institute. She became to be a full professor in Chemistry Department from 2013 at East China Normal University. Her research interests include catalytic selective conversion of bio-resource (lignin, pyrolysis bio-oil, lipid, and alcohol) to bio fuels and fine chemicals. The fundamental chemistry involved in these

processes is explored by kinetics in the elementary steps of the integrated catalytic processes and diverse ex situ and in situ characterization techniques on heterogeneous catalysts in gas phase and reactions in aqueous phase. Zhao has published more than 50 SCI indexed papers in recent years, which have been cited more than 2500 times with an H index of 25. She was granted with “Min Enze Energy and Chemical Engineering Award”, “the Recruitment Program of Global Young Experts”, “Shanghai Pujiang Program, “Young Scientist Award at 15th International Congress on Catalysis，and etc.

20

Renewable bubbles, bottles and (rubber) bands from biomass

Paul J. Dauenhauer Department of Chemical Engineering and Materials Science, University of Minnesota

hauer@umn.edu

Abstract: Thermochemical conversion of lignocellulosic biomass utilizes thermochemical

catalysts to transform sugars to the common chemicals comprising everyday products. In this work, sugars are catalytically transformed to many of the common chemicals and materials used in everyday products including PET plastics, surfactants and synthetic rubber. Novel solid acid catalysts and supported metals are utilized to promote catalytic dehydration and hydrogenation to selectively produce targeted compounds. In particular, Diels-Alder cycloaddition of furan dienes in tandem with sequential dehydration yields para-xylene. Acid-catalyzed acylation of furans with fatty acids (obtained from renewable oils) produces alkylfurans as precursors to novel surfactants. And selective hydrogenation and dehydration produce useful olefin precursors to synthetic rubbers. The presentation combines experiment and computation to identify the mechanisms of formation of various products by combining a variety of skills from the Catalysis Center for energy Innovation (www.efrc.udel.edu). Bio:

Paul J. Dauenhauer is the DuPont Young Professor and Associate Professor of Chemical Engineering and Materials Science at the University of Minnesota. He serves as Co-Director of the Catalysis Center for Energy Innovation. He received his B.S. in Chemical Engineering and Chemistry from the University of Wisconsin Madison and Ph.D. in Chemical Engineering from the University of Minnesota. He worked for the Dow Chemical Company as a Senior Research Engineer in Midland, MI, and Freeport, TX. His work on catalysis and reaction engineering of renewable feedstocks has

been highlighted by numerous awards including the DOE Early Career, NSF CAREER, the Rutherford Aris Excellence in Reaction Engineering Award, and the Camille Dreyfus Teacher-Scholar Award. His is the co-founder of Sironix Renewables and inventor of the flagship technology for Activated Research Company.

21

Converting of lignin into aromatics by tungsten carbide

Changzhi Li Dalian Institute of Chemical Physics, Dalian, China

licz@dicp.ac.cn Abstract:

Efficient catalytic conversion of lignin into aromatic chemicals through selective cleavage of the aryl ether bonds remains a huge challenge in catalysis due to the amorphous carbon-based inactive property and highly heterogeneous nature of lignin. In this lecture, we will discuss a remarkably effective method for the chemoselective C–O cleavage of typical β-O-4 model compounds and deconstruction of lignin feedstock with tungsten carbide catalyst (W2C/AC). Our results show that the conversion efficiency is determined in large extent by solvent effects, and is also affected by both electronic and steric effects for lignin model compounds. Mechanism study shows that W2C/AC catalyzed in-situ hydrogen transfer reaction from methanol to the substrate is responsible for the high performance in methanol solvent. The catalyst stability under liquid phase conditions will be discussed as well. Moreover, the correlation between different lignin structures and the depolymerized products was deeply studied through various characterizations. The above results are benefit for us to have a better understanding on the yield and distribution of phenolic products in relation to the structure of lignin; the high activity of W2C/AC provides us a strategy for the valorization of lignin using non-noble metal catalyst. Bio:

Changzhi Li received his Ph.D. degree in 2009 from Dalian Institute of Chemical Physics (DICP) under the supervision of Prof. Zongbao (kent) Zhao, then he joined Prof. Tao Zhang's group where he was promoted to an associated professor in 2012. In 2013, he won "Min Enze Energy and Chemical Engineering Award" jointly established by Chinese Academy of Engineering and Sinopec Group. He has published 25 papers on international journals including Chem. Rev., Energy Environ. Sci., Green Chem., etc. His current research focuses on the catalytic depolymerization of lignin and the production

of aromatic chemicals from bio-based compounds.

22

Strong metal-support interaction or “overcoat” enabled catalysts for efficient transformation of biomolecules

Fuwei Li State Key Laboratory for Oxo Synthesis and Selective Oxidation, Lanzhou Institute of

Chemical Physics, China fuweili@licp.cas.cn

Abstract: Unlike petroleum based raw materials, biomass feedstocks are highly

functionalized and thermally unstable, thus making them very difficult to be refined in the gas phase. So the upgrading is normally carried out in liquid phase reactions, wherein the heterogeneous metal catalysts are usually suffering from the irreversible deactivation problem caused by the leaching of active metal species into the solution. At the same time, the deactivation greatly impedes the utilization of a catalyst in industrial processes, in this sense, the catalyst stability is crucial to the economic and environmental sustainability of catalytic processes.

Catalytic conversion of LA into valued chemicals plays a key role in low carbon and sustainable biomass conversion, meanwhile, poses more challenge on the catalyst stability, due to the high activity or affinity of acid group toward the supported metal species under hydrothermal condition. To address this challenge, we fabricated chitosan derived Ru-Ni bimetallics catalyst in order mesoporous carbon, which gave high TOF valure (>2000 h-1) in the hydrogenation of LA intoγ-valerolactone within at least 15 runs. Further, a tandem transformation of LA into valeric biofuel could be achieved over an encapsulated Co@HZSM-5. The 1,4-pentanediol could be efficiently synthesized from LA in high selectivity over a copper based catalyst featuring strong metal-support interaction. We also interestingly found an alternative route to prepare pyrrolidone enabled by a carbon nanofilm coated Ni catalyst. Finally, our study on the catalytic conversion of furfural was also reported. Bio:

Fuwei Li completed his Ph.D. thesis in 2005 at Lanzhou Institute of Chemical Physics (LICP), Chinese Academy of Sciences (CAS). He subsequently became a research assistant at the Institute of Process Engineering of CAS. In the April of 2006, he moved to the National University of Singapore as a postdoctor fellow. Since 2010, he is a full professor at LICP and his research interests include advanced syntheses of bio-related chemicals and functional N-heterocycles. He had published over 60 research papers with 2000 plus citations.

23

The Importance of Puckering in Carbohydrate Conversion: It’s Elementary

Heather Mayes Chemical Engineering Department, University of Michigan, USA

hbmayes@umich.edu

Abstract: Understanding the molecular-level reactions can aid rational design of catalysts and

process optimization. However, this knowledge had remained elusive, despite decades of research into the chemical mechanisms governing its conversion. To solve these mysteries, we have simulated cellulose thermochemical and enzymatic conversion. The resulting models allow us to investigate complex reaction networks, determine elementary steps, calculate kinetic parameters, and predict macroscopic properties that can be compared with experimental data.

Our QM and QM/MM models of both thermochemical and enzymatic conversion allow identification of key features of the conversion pathways, particularly puckering of the ring conformation from the most stable 4C1 (equatorial chair) conformation to specific alternate geometries. The elucidation of elementary steps has provided the fundamental knowledge required to create microkinetic models of cellulose pyrolysis, including the effect of alkali ions, and suggested new avenues for rational enzyme design. Bio:

Heather Mayes joined the Chemical Engineering Department in January 2017 as an assistant professor. Her group, Team Mayes and Blue, uses multiscale modeling and enhanced sampling to understand protein-sugar interactions and harness them for renewable chemicals and improved health. These computational tools allow us to explore length and time scales generally too small to be experimentally observed. They allow us to learn how nature catalyzes reactions and then apply that learning to make more efficient enzymes and proteins for our use in biotechnology, such as more efficient conversion of

non-food biomass into valuable products. Dr. Mayes earned a bachelor’s degree in chemical engineering from the University

of Illinois at Chicago after first beginning her undergraduate studies at Harvard University. She then worked as a chemical engineering consultant, where she focused on process and kinetic modeling, before obtaining her PhD in Chemical Engineering from Northwestern University. Her graduate work focused on revealing fundamental reaction mechanisms governing thermochemical and enzymatic decomposition of cellulose. She was a Department of Energy Computation Scholar Graduate Fellow and completed a practicum at the National Renewable Energy Laboratory. As a postdoctoral scholar at the University of Chicago, she expanded her body of work to in developing methods for modeling reactions and in simulation transmembrane proteins. Heather has been active in outreach including sharing her research with underrepresented groups in engineering and encouraging them to consider careers in engineering, partnering with schools and the Society of Women Engineers.

24

Catalytic Conversion of Lignin Models and Extracts into Oxygenates

Feng Wang State Key Laboratory of Catalysis, Dalian National Laboratory for Clean Energy, Dalian

Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, China wangfeng@dicp.ac.cn

Abstract:

One of the challenges of depolymerizing lignin lies in the selective cleavage of C–O and/or C–C bonds of β-O-4 linkages in order to obtain valuable aromatic compounds. In recent years, we have developed several methods to achieve this goal. i) Two-step strategy for oxidative cleavage of lignin C–C bond to aromatic acids and phenols with molecular oxygen as oxidant. In the first step, lignin β-O-4 alcohol was oxidized to β-O-4 ketone over a VOSO4/TEMPO [(2,2,6,6-tetramethylpiperidin-1-yl)oxyl)] catalyst. In the second step, the C–C bond of β-O-4 linkages was selectively cleaved to acids and phenols by oxidation over a Cu/1,10-phenanthroline catalyst. Computational investigations suggested a copper-oxo-bridged dimer was the catalytically active site for hydrogen-abstraction from Cβ−H bond, which was the rate-determining step for the C–C bond cleavage. ii) A photocatalytic oxidation-hydrogenolysis tandem method for cleaving C–O bond of β-O-4 lignin models via double light wavelength switching (DLWS) strategy. We also reveal that the in-situ-formed Ti3+ is responsible for the photocatalytic hydrogenolysis through electron transfer from Ti3+ to β-O-4 linkages. The Pd/ZnIn2S4 catalyst is used in the aerobic oxidation of α-C–OH of β-O-4 to α-C=O under 455-nm light, and then a TiO2-NaOAc system is utilized for cleaving C–O bond neighbor to the α-C=O through hydrogenolysis reaction under 365-nm light. iii) A photocatalytic strategy for β-hydroxyl C–C bond cleavage to aromatic aldehyde with high selectivity through an abstracted hydrogen mechanism over highly dispersed copper and ceria catalyst. These studies combine the experimental and theoretical together to deepen the understanding of the β-O-4 linkage cleavage. Bio:

Feng Wang obtained his Ph.D. in Physical Chemistry from Dalian Institute of Chemical Physics, CAS, in 2005. From 2005-2009, he conducted his postdoctoral research at University of California (Berkeley) with Alexandar Katz and Enrique Iglesia, and at Catalysis Research Center of Hokkaido Unviersity with Wataru Ueda and Rye Abe. In December 2009, Dr. Wang joined Dalian Institite of Chemical Physics as an associate profesor. He became a Full-professor in 2012 under the financial support of 100-talent plan of CAS. He is also a joint professor with Dalian University of Technology since 2016 under the support of

Changjiang Youth Scholar. Dr. Wang is the recipient of Outstanding Young Scientist Foundation (2014) and Young Scientist Award (2012). He has published 46 papers since 2009 and filed 40 patents. His research interests include synthesis of nanometal and nanometal oxides with special size and morphology, study the chemical nature of defects in metals and metal oxides and novel strategies for the conversion of biomass to value-added products.