Author Archives: Carl Menning

Nominees For 2018–2019 CCP Officers

Nominees for Chair Elect

Marat Ora­zov

Marat Ora­zov obtained his B.S. degree in Chem­i­cal Engi­neer­ing in 2012, at the Uni­ver­si­ty of Cal­i­for­nia, Berke­ley, hav­ing per­formed under­grad­u­ate research in the labs of Profs. Alexan­der Katz and David B. Graves. Then, under the guid­ance of Prof. Mark E. Davis, he pur­sued a Ph.D. in Chem­i­cal Engi­neer­ing at Cal­tech, where he stud­ied a num­ber of cat­alyt­ic sys­tems per­tain­ing to the syn­the­sis of valu­able chem­i­cals from bio­mass. In the fall of 2016, Dr. Ora­zov start­ed his post­doc­tor­al research with Prof. Thomas F. Jaramil­lo, at Stan­ford, devel­op­ing ther­mo­cat­alyt­ic sys­tems for the syn­the­sis of high­er alco­hols and cath­ode elec­tro­cat­a­lysts for hydro­gen fuel cells. In the sum­mer of 2018, he will join the fac­ul­ty as an Assis­tant Pro­fes­sor, at the Depart­ment of Chem­i­cal & Bio­mol­e­c­u­lar Engi­neer­ing, at the Uni­ver­si­ty of Delaware. He aims to study and devel­op mate­ri­als and cou­pled cat­alyt­ic sys­tems for the renew­able gen­er­a­tion and stor­age of ener­gy, and chem­i­cal syn­the­sis, with par­tic­u­lar inter­est in micro­p­orous mate­ri­als and elec­tro­chem­istry.

Jacob Dick­in­son

Jake start­ed at DuPont 2014. He has worked on a vari­ety of projects includ­ing the con­ver­sion of non-edi­ble bio­mass into an inter­me­di­ate for renew­able monomers, devel­op­ment of ther­mo­plas­tic com­pos­ites for com­pressed hydro­gen stor­age ves­sels, and, most recent­ly, on monomer and poly­mer process devel­op­ment.

Pri­or to join­ing DuPont, Jake attend­ed Hope Col­lege and grad­u­at­ed with a B.S. in Chem­i­cal Engi­neer­ing, and then went on to the Uni­ver­si­ty of Michi­gan and grad­u­at­ed with a Ph.D. in Chem­i­cal Engi­neer­ing. The gen­er­al focus of his the­sis was the hydrodeoxy­gena­tion of phe­nols in super­crit­i­cal water. A major con­tri­bu­tion of his the­sis was the syn­the­sis and use of a Cu-doped Raney Ni cat­a­lyst that con­tained tun­able HDO and gasi­fi­ca­tion activ­i­ty depend­ing on the Cu con­tent of the cat­a­lyst.

Jake served as the Mem­ber­ship Direc­tor dur­ing the 2016–17 CCP sea­son and hopes to con­tin­ue serv­ing the catal­y­sis com­mu­ni­ty.

Nominees for Treasurer

Lifeng Wang

Lifeng Wang is a research chemist in Zeolyst Inter­na­tion­al and his research work is focused on devel­op­ing var­i­ous zeo­lite cat­a­lysts for auto­mo­tive appli­ca­tions. He received his BS and PhD in Chem­istry from Jilin Uni­ver­si­ty, Chi­na, where his research was focused on design and syn­the­sis of nov­el sor­bents and cat­a­lysts includ­ing sil­i­cas, car­bons and zeo­lites. Lifeng has been an active mem­ber of the Catal­y­sis Club of Philadel­phia since 2014.

Ist­van Halasz

Ist­van is Prin­ci­pal Chemist at the Research & Devel­op­ment Cen­ter of PQ Cor­po­ra­tion, study­ing the struc­ture and prop­er­ties of sil­i­ca-deriv­a­tives. Pri­or to this he stud­ied cat­alyt­ic process­es and super­con­duct­ing ceram­ics part­ly at US uni­ver­si­ties and part­ly at the Cen­tral Chem­istry Insti­tute of the Hun­gar­i­an Acad­e­my of Sci­ences. From this lat­ter insti­tu­tion he obtained a Ph. D. equiv­a­lent degree and also holds a doc­tor­ate degree from the Lajos Kos­suth Uni­ver­si­ty (Hun­gary). In the ini­tial 12 years of his research car­ri­er he worked at the Hun­gar­i­an Hydro­car­bon Insti­tute, devel­op­ing and scal­ing-up effi­cient patent­ed process­es for phar­ma­ceu­ti­cal, fine chem­i­cal and petro­chem­i­cal indus­tries along with per­form­ing fun­da­men­tal stud­ies in acid-base catal­y­sis. He served as pres­i­dent and chair in var­i­ous sci­en­tif­ic orga­ni­za­tions, edit­ed one book, authored cir­ca 125 book chap­ters, papers and patents and held 90+ con­fer­ence pre­sen­ta­tions.

Nominees for Director (Poster, Membership and Sponsorship)

Run­bo Li

Run­bo Li obtained her Ph.D. in Ana­lyt­i­cal Chem­istry from Drex­el Uni­ver­si­ty in USA. In her the­sis, she stud­ied dif­fer­ent meth­ods for prepar­ing sam­ples for analy­sis by MALDI TOFMS and applied these meth­ods to quan­ti­fy pro­teins. At PQ R&D, she has focused on ana­lyt­i­cal method devel­op­ment and char­ac­ter­i­za­tion research relat­ed to sil­i­cates, glass beads, amor­phous sil­i­ca gel and zeo­lites. She has pub­lished 18 papers.

Nicholas McNa­ma­ra

Nicholas McNa­ma­ra attained a B.S. (2009) and M.S. (2011) from the Uni­ver­si­ty of Day­ton where he car­ried out research on the sono­chem­i­cal syn­the­sis and char­ac­ter­i­za­tion of car­bon-sup­port­ed met­al nanopar­ti­cles. He then attend­ed the Uni­ver­si­ty of Notre Dame where his grad­u­ate research was sup­port­ed by the Patrick and Jana Eil­ers Grad­u­ate Stu­dent Fel­low­ship for Ener­gy Relat­ed Research. In his grad­u­ate research, he stud­ied the syn­the­sis, char­ac­ter­i­za­tion, and uti­liza­tion of met­al-organ­ic frame­works (MOFs) and MOF-tem­plat­ed mate­ri­als as oxida­tive desul­fu­r­iza­tion cat­a­lysts. He earned his PhD in 2015 under the direc­tion of Prof. Jason Hicks. He began his indus­tri­al research career in 2016 as a staff sci­en­tist in the Clean Air divi­sion of John­son Matthey. His cur­rent research focus­es on the design of new mate­ri­als for tar­get­ed emis­sions con­trol appli­ca­tions and the deter­mi­na­tion of struc­ture-prop­er­ty rela­tion­ships.

Bill Borghard

Cur­rent­ly, Bill is a con­sul­tant in the area of catal­y­sis. In par­tic­u­lar, he is the indus­tri­al liai­son for the Rut­gers Cat­a­lyst Man­u­fac­tur­ing Con­sor­tium, based in the Chem­i­cal and Bio­chem­i­cal Engi­neer­ing Depart­ment at Rut­gers Uni­ver­si­ty. He is also on the Advi­so­ry Board for the Catal­y­sis Cen­ter for Ener­gy Inno­va­tion (CCEI), based at the Uni­ver­si­ty of Delaware.

Bill retired from Exxon­Mo­bil in 2013 after 32 years with the com­pa­ny. He start­ed at the Mobil Pauls­boro Lab in 1980 inves­ti­gat­ing Fis­ch­er-Trop­sch/ZSM-5 two-stage wax upgrad­ing. In 1982, Bill trans­ferred to Mobil’s lab in Prince­ton work­ing in explorato­ry research and lab automa­tion. In 1992, Bill returned to Pauls­boro, where he had assign­ments in reform­ing, light gas upgrad­ing, and cat­a­lyst char­ac­ter­i­za­tion. Sub­se­quent­ly, he moved to the Clin­ton labs of Exxon­Mo­bil, where he led a num­ber of major R&D projects, includ­ing GTL cat­a­lyst devel­op­ment, nov­el diesel cat­a­lysts, Algae Bio­Fu­els, and resid upgrad­ing. Bill is an inven­tor or co-inven­tor on 24 U.S. patents.

Pri­or to join­ing Mobil, Bill grad­u­at­ed from Stan­ford Uni­ver­si­ty with a Ph.D. in chem­i­cal engi­neer­ing under the tute­lage of Michel Boudart. He also obtained and M.S. and B.S. in chem­i­cal engi­neer­ing from the Uni­ver­si­ty of Con­necti­cut where he stud­ied under C.O. Ben­nett. He vol­un­teers for Seeds of Hope Min­istries (Cam­den, NJ).

Jim Hugh­es

Jim Hugh­es com­plet­ed obtained his bach­e­lors of Sci­ence from the Uni­ver­si­ty of Cal­i­for­nia, Los Ange­les in Chem­istry (UCLA). After grad­u­a­tion he spent two years work­ing in the Catal­y­sis Devel­op­ment group at Chevron’s R&D cen­ter in Rich­mond Cal­i­for­nia work­ing on het­ero­ge­neous cat­a­lyst devel­op­ment. After­wards Jim left Chevron to pur­sue his Ph.D. under the guid­ance of Alexan­dra Navrot­sky at The Uni­ver­si­ty of Cal­i­for­nia, Davis. Jim’s Ph.D. was the study of the Ther­mo­dy­nam­ics of Met­al-Organ­ic Frame­works. Dur­ing his Ph.D. Jim was award­ed a NSF-EASPI fel­low­ship. Cur­rent­ly Jim Is a Senior Research Chemist with Zeolyst Inter­na­tion­al, work­ing on pilot scale syn­the­sis and com­mer­cial pro­duc­tion of zeo­lite mol­e­c­u­lar sieves.

Renewable Isoprene By Sequential Hydrogenation of Itaconic Acid and Dehydra-Decyclization of 3-Methyl-Tetrahydrofuran

2018 Spring Symposium

Omar Abdel­rah­man, Post-Doc, Paul Dauen­hauer Group, Depart­ment of Chem­i­cal Engi­neer­ing & Mate­r­i­al Sci­ence, Uni­ver­si­ty of Min­neso­ta, 421 Wash­ing­ton Ave. SE, Min­neapo­lis, MN 55455

Abstract — The cat­alyt­ic con­ver­sion of bio­mass-derived feed­stocks to val­ue added chem­i­cals is an impor­tant chal­lenge to alle­vi­ate the depen­dence on petro­le­um-based resources. To accom­plish this, the inher­ent­ly high oxy­gen con­tent of bio­mass com­pounds, such as that of lig­no­cel­lu­losic bio­mass, requires sig­nif­i­cant reduc­tion via hydrodeoxy­gena­tion strate­gies. The unsat­u­rat­ed car­boxylic acid ita­con­ic acid (IA) can be pro­duced from bio­mass via fer­men­ta­tion path­ways, for exam­ple. A path­way of inter­est is the con­ver­sion of IA to iso­prene, facil­i­tat­ing the renew­able pro­duc­tion of an indus­tri­al­ly rel­e­vant diolefin. IA can be suc­ces­sive­ly hydro­genat­ed to yield 3-methyl tetrahy­dro­fu­ran (3-MTHF), in a one-pot cas­cade reac­tion, where a Pd-Re bimetal­lic cat­a­lyst results in an 80% yield to 3-MTHF. The 3-MTHF can then be con­vert­ed to iso­prene, and oth­er pen­ta­di­enes, through an acid cat­alyzed vapor-phase dehy­dra-decy­cliza­tion. Mul­ti­ple sol­id acid cat­a­lysts, includ­ing alu­mi­nosil­i­cates, met­al oxides and phos­pho­rous mod­i­fied zeo­lites, were screened for the dehy­dra-decy­cliza­tion step. A new class of cat­alyt­ic mate­ri­als, all sil­i­con
phos­pho­rous con­tain­ing zeo­lites, were found to be the most selec­tive (70% iso­prene and 20% pen­ta­di­enes), where the major side reac­tion involved is a retro-prins con­den­sa­tion of 3-MTHF to butane and formalde­hyde. Through kinet­ic stud­ies, an inves­ti­ga­tion into the effect of Brøn­st­ed acid strength, pore size and oper­at­ing con­di­tions on the selec­tiv­i­ty to iso­prene are dis­cussed. The prospect of apply­ing this dehy­dra-decy­cliza­tion strat­e­gy to oth­er sat­u­rat­ed cyclic ethers will also be dis­cussed, which enables the pro­duc­tion of oth­er diolefin mol­e­cules of inter­est such as buta­di­ene and lin­ear pen­ta­di­enes.

[1] Abdel­rah­man, O. A.; Park, D. S.; Vin­ter, K. P.; Span­jers, C. S.; Ren, L.; Cho, H. J.; Zhang, K.; Fan, W.; Tsap­at­sis, M.; Dauen­hauer, P. J. ACS Catal. 2017, 7, 1428–1431.

Using Water as a Co-catalyst in Heterogeneous Catalysis to Improve Activity and Selectivity

2018 Spring Symposium

Lars C. Grabow, Depart­ment of Chem­i­cal and Bio­mol­e­c­u­lar Engi­neer­ing, Uni­ver­si­ty of Hous­ton, Hous­ton, TX 77204–4004, USA

Abstract — “What hap­pens when you add water?” is pos­si­bly the most fre­quent­ly asked ques­tion after pre­sen­ta­tions in het­ero­ge­neous catal­y­sis. In this talk, I will demon­strate that this ques­tion is indeed para­mount and that the pres­ence of even minute amounts of water can dras­ti­cal­ly change reac­tion rates and prod­uct selec­tiv­i­ties. Exam­ples include water-medi­at­ed pro­ton hop­ping across a met­al-oxide sur­face, oxi­da­tion of car­bon monox­ide at the gold/titania inter­face, and hydrodeoxy­gena­tion of phe­no­lic com­pounds over tita­nia sup­port­ed ruthe­ni­um cat­a­lysts. Togeth­er, these exam­ples demon­strate that water can act as co-cat­a­lyst in a vari­ety of cat­alyt­ic reac­tions and by vary­ing the amount of water it may be pos­si­ble to tune reac­tion rates and prod­uct selec­tiv­i­ty.

Selective Catalytic Oxidation of Alcohols over Supported Metal Nanoparticles and Atomically-Dispersed Metal Cations

2018 Spring Symposium

Robert J. Davis, Depart­ment of Chem­i­cal Engi­neer­ing, Uni­ver­si­ty of Vir­ginia, Char­lottesville, VA, USA

Abstract — Selec­tive oxi­da­tion of alco­hols to car­bonyl com­pounds is an impor­tant reac­tion in organ­ic syn­the­sis and will like­ly play a sig­nif­i­cant role in the devel­op­ment of val­ue-added chem­i­cals from bio­mass. The indus­tri­al appli­ca­tion of a pre­cious met­al cat­a­lyst such as Pt, how­ev­er, can be hin­dered by deac­ti­va­tion and high price. We have there­fore explored the mode of deac­ti­va­tion dur­ing alco­hol oxi­da­tion on Pt by in-situ spec­troscopy and stud­ied the role of var­i­ous pro­mot­ers on cat­a­lyst per­for­mance. Results con­firm that slow decar­bony­la­tion of prod­uct alde­hyde deposit­ed unsat­u­rat­ed hydro­car­bon on the sur­face that blocked access to the active sites. Addi­tion of Bi as a pro­mot­er did not pre­vent the decar­bony­la­tion side reac­tion, but instead enhanced the acti­va­tion of dioxy­gen dur­ing the cat­alyt­ic cycle. In an effort to avoid the use of pre­cious met­als alto­geth­er, the oxi­da­tion of alco­hols over atom­i­cal­ly-dis­persed, non-pre­cious met­al cations (Fe, Cu, and Co) locat­ed in a nitro­gen-doped car­bon matrix was demon­strat­ed. Exten­sive char­ac­ter­i­za­tion of these non-pre­cious met­al cat­a­lysts revealed impor­tant insights into the oxi­da­tion mech­a­nism and sta­bil­i­ty of this new class of atom­i­cal­ly-dis­persed met­al cat­a­lyst.

Tuning the Electrocatalytic Oxygen Reduction Reaction Activity of PtCo Nanocrystals by Cobalt Concentration and Phase Transformation Methods

2018 Spring Symposium

Jen­nifer D. Lee, Ph.D. Can­di­date, Christo­pher B. Mur­ray Group, Depart­ment of Chem­istry, Uni­ver­si­ty of Penn­syl­va­nia

Abstract — The pro­ton exchange mem­brane fuel cell (PEMFC) is a crit­i­cal tech­nol­o­gy to enhance the clean, sus­tain­able pro­duc­tion and usage of ener­gy, but prac­ti­cal appli­ca­tion remains chal­leng­ing because of the high cost and low dura­bil­i­ty of the cath­ode cat­a­lysts that per­form oxy­gen reduc­tion reac­tion (ORR). Efforts have been placed on the study of intro­duc­ing first-row tran­si­tion met­als in Pt-M alloys to reduce the Pt load­ing and mod­u­late geo­met­ric, struc­tur­al and elec­tron­ic effects. To fur­ther improve the ORR reac­tion rate and cat­a­lysts sta­bil­i­ty, alloys that adopt an inter­metal­lic struc­ture, espe­cial­ly the tetrag­o­nal L10-PtM phase, has been one of the most promis­ing mate­ri­als. In this con­tri­bu­tion, monodis­perse PtCo nanocrys­tals (NCs) with well-defined size and Co com­po­si­tion are syn­the­sized via solvother­mal meth­ods. The trans­for­ma­tion from face-cen­tered cubic (fcc) to ordered face-cen­tered tetrag­o­nal (fct) struc­ture was achieved via ther­mal anneal­ing. Depend­ing on the selec­tion of trans­for­ma­tion meth­ods, dif­fer­ent degrees of order­ing were intro­duced and fur­ther cor­re­lat­ed with their ORR per­for­mance. A detailed study of the anneal­ing tem­per­a­ture and com­po­si­tion depen­dent degree of order­ing is also high­light­ed. This work pro­vides the insight of dis­cov­er­ing the opti­mal spa­tial dis­tri­b­u­tions of the ele­ments at the atom­ic lev­el to achieve enhanced ORR activ­i­ty and sta­bil­i­ty.

Commercial Perspective of Alternative Routes to Acrylic Acid Monomer

2018 Spring Symposium

Jin­suo Xu, The Dow Chem­i­cal Com­pa­ny, 400 Arco­la Rd, Col­legeville, PA 19426

Abstract — Acrylic acid and cor­re­spond­ing acry­lates are major monomers for a vari­ety of func­tion­al poly­mers used broad­ly in our dai­ly life such as coat­ing, sealant, and per­son­al care. The two-stage selec­tive oxi­da­tion of propy­lene to acrolein and then to acrylic acid was first com­mer­cial­ized in ear­ly 70s and quick­ly became the dom­i­nant route to acrylic acid. Dri­ven by feed­stock cost or avail­abil­i­ty or sus­tain­abil­i­ty, sig­nif­i­cant efforts from both indus­try and acad­e­mia were devot­ed to devel­op­ing alter­na­tive routes to acrylic acid. Cat­a­lyst plays crit­i­cal role in the key step of trans­form­ing dif­fer­ent raw mate­r­i­al into prod­uct effec­tive­ly, for exam­ple, mixed met­al oxides MoVTeN­bOx in propane selec­tive oxi­da­tion, sol­id acids in dehy­dra­tion of glyc­erin or 3-HP, and var­i­ous oxides in aldol con­den­sa­tion of acetic acid and formalde­hyde. This pre­sen­ta­tion will dis­cuss the progress of these major routes, the chal­lenges towards com­mer­cial­iza­tion, and poten­tial solu­tions.

Mechanisms, active intermediates, and descriptors for epoxidation rates and selectivities on dispersed early transition metals

2018 Spring Symposium

Daniel Bre­gante, Alay­na John­son, Ami Patel, David Fla­her­ty, Depart­ment of Chem­i­cal and Bio­mol­e­c­u­lar Engi­neer­ing, Uni­ver­si­ty of Illi­nois, Urbana-Cham­paign

Abstract — Ear­ly tran­si­tion met­al atoms (groups IV-VI) dis­persed on sil­i­ca and sub­sti­tut­ed into zeo­lites effec­tive­ly cat­alyze the epox­i­da­tion of alkenes with hydro­gen per­ox­ide or alkyl per­ox­ide reac­tants, yet the under­ly­ing prop­er­ties that deter­mine the selec­tiv­i­ties and turnover rates of these cat­a­lysts are unclear. Here, a com­bi­na­tion of kinet­ic, ther­mo­dy­nam­ic, and in situ spec­tro­scop­ic mea­sure­ments show that when group IV — VI tran­si­tion met­als are dis­persed on sil­i­ca or sub­sti­tut­ed into zeo­lite *BEA, the met­als that form the most elec­trophilic sites give greater selec­tiv­i­ties and rates for the desired epox­i­da­tion path­way and present small­er enthalpic bar­ri­ers for both epox­i­da­tion and H2O2 decom­po­si­tion reac­tions.

In situ UV–vis spec­troscopy shows that these group IV and V mate­ri­als acti­vate H2O2 to form pools of hydroper­ox­ide and per­ox­ide inter­me­di­ates. Time-resolved UV–vis mea­sure­ments and the iso­mer­ic dis­tri­b­u­tions of cis-stil­bene epox­i­da­tion prod­ucts sug­gest that the active species for epox­i­da­tions on group IV and V tran­si­tion met­als are only M-OOH and M-(O2)2– species, respec­tive­ly. Mech­a­nis­tic inter­pre­ta­tions of turnover rates show that these group IV and V mate­ri­als cat­alyze epox­i­da­tions (e.g., of cyclo­hex­ene, styrene, and 1-octene) and H2O2 decom­po­si­tion through sim­i­lar mech­a­nisms that involve the irre­versible acti­va­tion of coor­di­nat­ed H2O2 fol­lowed by reac­tion with an olefin or H2O2. Epox­i­da­tion rates and selec­tiv­i­ties vary over five- and two-orders of mag­ni­tude, respec­tive­ly, among these cat­a­lysts and depend expo­nen­tial­ly on both the ener­gy for lig­and-to-met­al charge trans­fer (LMCT) and chem­i­cal probes of the dif­fer­ence in Lewis acid strength between met­al cen­ters. Togeth­er, these obser­va­tions show that more elec­trophilic active-oxy­gen species (i.e., low­er-ener­gy LMCT) are more reac­tive and selec­tive for epox­i­da­tions of elec­tron-rich olefins. The micro­p­ores of zeo­lites about active sites can serve to pref­er­en­tial­ly sta­bi­lize reac­tive states that lead to epox­i­da­tions by chang­ing the mean diam­e­ter of the pore or the den­si­ty of near­by silanol groups. Con­se­quent­ly, these prop­er­ties pro­vide oppor­tu­ni­ties to increase rates of epox­ide for­ma­tion over that with­in meso­porous sil­i­cas. Con­sis­tent­ly, H2O2 decom­po­si­tion rates pos­sess a weak­er depen­dence on the elec­trophilic­i­ty of the active sites and the sur­round­ing pore envi­ron­ment, which indi­cates that cat­a­lysts with both greater rates and selec­tiv­i­ties may be designed fol­low­ing these struc­ture-func­tion rela­tion­ships.