skip to main content
US FlagAn official website of the United States government
dot gov icon
Official websites use .gov
A .gov website belongs to an official government organization in the United States.
https lock icon
Secure .gov websites use HTTPS
A lock ( lock ) or https:// means you've safely connected to the .gov website. Share sensitive information only on official, secure websites.


Title: Tetrapyrrolic Surface Coatings for Applications in Photoelectrosynthetic Fuel Production
Hybrid materials capable of linking light capture and conversion technologies with the ability to drive reductive chemical transformations are attractive as components in photoelectrosynthetic cells. [1] We have recently reported methods of applying molecular surface coatings composed of metalloporphyrin redox catalysts onto solid-state substrates that are either conductive or semi-conductive. [2-5] The metalloporphyrin catalysts used in this work are capable of activating electrochemical transformations including the conversion of protons to hydrogen and carbon dioxide to carbon monoxide. In one approach, metalloporphyrin precursors are prepared via a novel synthetic strategy to yield a macrocycle with a pendent 4-vinylphenyl surface attachment group at the beta-position of the porphyrin ring structure. [2] This modification allows use of a photo-induced immobilization chemistry to attach intact metalloporphyrins to a range of (semi)conducting surfaces. In addition, we have shown that initial application of thin-film polymer surface coatings can provide a molecular interface for assembling metalloporphyrin catalysts in a subsequent wet chemical treatment step. [3] In this presentation, spectroscopic characterization of these materials coupled with electrochemical analysis will be presented. These findings offer an improved understanding of the structure and function relationships governing this class of materials. 1. A. M. Beiler, D. Khusnutdinova, S. I. Jacob, G. F. Moore, Ind. & Eng. Chem. Research, 55, 5306-5314 (2016); DOI: 10.1021/acs.iecr.6b00478 2. D. Khusnutdinova, A. M. Beiler, B. L. Wadsworth, S. I. Jacob, G. F. Moore, Chem. Sci., 8, 253-259 (2017); DOI: 10.1039/c6sc02664h 3. A. M. Beiler, D. Khusnutdinova, B. L. Wadsworth, G. F. Moore, Inorg. Chem., 56, 12178 (2017); DOI: 10.1021/acs.inorgchem.7b01509 4. A. M. Beiler, D. Khusnutdinova, S. I. Jacob, G. F. Moore, ACS Appl. Mater. Interfaces, 8, 10038-10043 (2016); DOI: 10.1021/acsami.6b01557 5. B. L. Wadsworth, A. M. Beiler, D. Khusnutdinova, S. I. Jacob, G. F. Moore, ACS Catal. 6, 8048-8057 (2016); DOI: 10.1021/acscatal.6b02194  more » « less
Award ID(s):
1653982
PAR ID:
10082155
Author(s) / Creator(s):
; ; ;
Date Published:
Journal Name:
ECS Meeting Abstracts
Issue:
MA2018-01
Page Range / eLocation ID:
972
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. A s a c om pl e men t t o da ta d edupli cat ion , de lta c om p ress i on fu r- t he r r edu c es t h e dat a vo l u m e by c o m pr e ssi n g n o n - dup li c a t e d ata chunk s r e l a t iv e to t h e i r s i m il a r chunk s (bas e chunk s). H ow ever, ex is t i n g p o s t - d e dup li c a t i o n d e l t a c o m pr e ssi o n a p- p ro a ches fo r bac kup s t or ag e e i t h e r su ffe r f ro m t h e l ow s i m - il a r i t y b e twee n m any de te c ted c hun ks o r m i ss so me po t e n - t i a l s i m il a r c hunks , o r su ffer f r om l ow (ba ckup and r es t ore ) th r oug hpu t du e t o extr a I/ Os f or r e a d i n g b a se c hun ks o r a dd a dd i t i on a l s e r v i c e - d i s r up t ive op e r a t i on s to b a ck up s ys t em s. I n t h i s pa p e r, w e pr opo se L oop D e l t a t o a dd ress the above - m e n t i on e d prob l e m s by an e nha nced em b e ddi n g d e l t a c o m p - r e ss i on sc heme i n d e dup li c a t i on i n a non - i n t ru s ive way. T h e e nha nce d d elt a c o mpr ess ion s che m e co m b in e s f our key t e c h - ni qu e s : (1) du a l - l o c a li t y - b a s e d s i m il a r i t y t r a c k i n g to d e t ect po t e n t i a l si m il a r chun k s b y e x p l o i t i n g both l o g i c a l and ph y - s i c a l l o c a li t y, ( 2 ) l o c a li t y - a wa r e pr e f e t c h i n g to pr efe tc h ba se c hun ks to a vo i d ex t ra I/ Os fo r r e a d i n g ba s e chun ks on t h e w r i t e p at h , (3) c a che -aware fil t e r to avo i d ext r a I/Os f or b a se c hunk s on t he read p at h, a nd (4) i nver sed de l ta co mpressi on t o perf orm de lt a co mpress i o n fo r d at a chunk s t hat a re o th e r wi se f o r b i dd e n to s er ve as ba se c hunk s by r ew r i t i n g t e c hn i qu e s d e s i g n e d t o i m p r ove r es t o re pe rf o rma nc e. E x p e r i m e n t a l re su lts indi ca te t hat L oop D e l t a i ncr ea se s t he c o m pr e ss i o n r a t i o by 1 .2410 .97 t i m e s on t op of d e dup li c a - t i on , wi t hou t no t a b l y a ffe c t i n g th e ba ck up th rou ghpu t, a nd i t i m p r ove s t he res to re p er fo r m an ce b y 1.23.57 t i m e 
    more » « less
  2. F or c e d at a f or a fl a p pi n g f oil e n er g y h ar v e st er wit h a cti v e l e a di n g e d g e m oti o n o p er ati n g i n t h e l o w r e d u c e d fr e q u e n c y r a n g e i s c oll e ct e d t o d et er mi n e h o w l e a di n g e d g e m oti o n aff e ct s e n er g y h ar v e sti n g p erf or m a n c e. T h e f oil pi v ot s a b o ut t h e mi dc h or d a n d o p er at e s i n t h e l o w r e d u c e d fr e q u e n c y r a n g e of 𝑓𝑓 𝑓𝑓 / π‘ˆπ‘ˆ ∞ = 0. 0 6 , 0. 0 8, a n d 0. 1 0 wit h 𝑅𝑅 𝑅𝑅 = 2 0 ,0 0 0 βˆ’ 3 0 ,0 0 0 , wit h a pit c hi n g a m plit u d e of πœƒπœƒ 0 = 7 0 ∘ , a n d a h e a vi n g a m plit u d e of β„Ž 0 = 0. 5 𝑓𝑓 . It i s f o u n d t h at l e a di n g e d g e m oti o n s t h at r e d u c e t h e eff e cti v e a n gl e of att a c k e arl y t h e str o k e w or k t o b ot h i n cr e a s e t h e lift f or c e s a s w ell a s s hift t h e p e a k lift f or c e l at er i n t h e fl a p pi n g str o k e. L e a di n g e d g e m oti o n s i n w hi c h t h e eff e cti v e a n gl e of att a c k i s i n cr e a s e d e arl y i n t h e str o k e s h o w d e cr e a s e d p erf or m a n c e. I n a d diti o n a di s cr et e v ort e x m o d el wit h v ort e x s h e d di n g at t h e l e a di n g e d g e i s i m pl e m e nt f or t h e m oti o n s st u di e d; it i s f o u n d t h at t h e m e c h a ni s m f or s h e d di n g at t h e l e a di n g e d g e i s n ot a d e q u at e f or t hi s p ar a m et er r a n g e a n d t h e m o d el c o n si st e ntl y o v er pr e di ct s t h e a er o d y n a mi c f or c e s. 
    more » « less
  3. A gr e at d e al of i nt er e st s urr o u n d s t h e u s e of tr a n s cr a ni al dir e ct c urr e nt sti m ul ati o n (t D C S) t o a u g m e nt c o g niti v e tr ai ni n g. H o w e v er, eff e ct s ar e i n c o n si st e nt a cr o s s st u di e s, a n d m et aa n al yti c e vi d e n c e i s mi x e d, e s p e ci all y f o r h e alt h y, y o u n g a d ult s. O n e m aj or s o ur c e of t hi s i n c o n si st e n c y i s i n di vi d u al diff er e n c e s a m o n g t h e p arti ci p a nt s, b ut t h e s e diff er e n c e s ar e r ar el y e x a mi n e d i n t h e c o nt e xt of c o m bi n e d tr ai ni n g/ sti m ul ati o n st u di e s. I n a d diti o n, it i s u n cl e ar h o w l o n g t h e eff e ct s of sti m ul ati o n l a st, e v e n i n s u c c e s sf ul i nt er v e nti o n s. S o m e st u di e s m a k e u s e of f oll o w- u p a s s e s s m e nt s, b ut v er y f e w h a v e m e a s ur e d p erf or m a n c e m or e t h a n a f e w m o nt hs aft er a n i nt er v e nti o n. H er e, w e utili z e d d at a fr o m a pr e vi o u s st u d y of t D C S a n d c o g niti v e tr ai ni n g [ A u, J., K at z, B., B u s c h k u e hl, M., B u n arj o, K., S e n g er, T., Z a b el, C., et al. E n h a n ci n g w or ki n g m e m or y tr ai ni n g wit h tr a n scr a ni al dir e ct c urr e nt sti m ul ati o n. J o u r n al of C o g niti v e N e u r os ci e n c e, 2 8, 1 4 1 9 – 1 4 3 2, 2 0 1 6] i n w hi c h p arti ci p a nts tr ai n e d o n a w or ki n g m e m or y t as k o v er 7 d a y s w hil e r e c ei vi n g a cti v e or s h a m t D C S. A n e w, l o n g er-t er m f oll o w- u p t o a ss es s l at er p erf or m a n c e w a s c o n d u ct e d, a n d a d diti o n al p arti ci p a nt s w er e a d d e d s o t h at t h e s h a m c o n diti o n w a s b ett er p o w er e d. W e a s s e s s e d b a s eli n e c o g niti v e a bilit y, g e n d er, tr ai ni n g sit e, a n d m oti v ati o n l e v el a n d f o u n d si g nifi c a nt i nt er a cti o ns b et w e e n b ot h b as eli n e a bilit y a n d m oti v ati o n wit h c o n diti o n ( a cti v e or s h a m) i n m o d els pr e di cti n g tr ai ni n g g ai n. I n a d diti o n, t h e i m pr o v e m e nt s i n t h e a cti v e c o nditi o n v er s u s s h a m c o n diti o n a p p e ar t o b e st a bl e e v e n a s l o n g a s a y e ar aft er t h e ori gi n al i nt er v e nti o n. β–  
    more » « less
  4. null (Ed.)
    A s m or e e d u c at or s i nt e gr at e t h eir c urri c ul a wit h o nli n e l e ar ni n g, it i s e a si er t o cr o w d s o ur c e c o nt e nt fr o m t h e m. Cr o w ds o ur c e d t ut ori n g h a s b e e n pr o v e n t o r eli a bl y i n cr e a s e st u d e nt s’ n e xt pr o bl e m c orr e ct n e s s. I n t hi s w or k, w e c o n fir m e d t h e fi n di n g s of a pr e vi o u s st u d y i n t hi s ar e a, wit h str o n g er c o n fi d e n c e m ar gi n s t h a n pr e vi o u sl y, a n d r e v e al e d t h at o nl y a p orti o n of cr o w d s o ur c e d c o nt e nt cr e at or s h a d a r eli a bl e b e n e fit t o st ud e nt s. F urt h er m or e, t hi s w or k pr o vi d e s a m et h o d t o r a n k c o nt e nt cr e at or s r el ati v e t o e a c h ot h er, w hi c h w a s u s e d t o d et er mi n e w hi c h c o nt e nt cr e at or s w er e m o st eff e cti v e o v er all, a n d w hi c h c o nt e nt cr e at or s w er e m o st eff e cti v e f or s p e ci fi c gr o u p s of st u d e nt s. W h e n e x pl ori n g d at a fr o m Te a c h er A SSI S T, a f e at ur e wit hi n t h e A S SI S T m e nt s l e ar ni n g pl atf or m t h at cr o w d s o ur c e s t ut ori n g fr o m t e a c h er s, w e f o u n d t h at w hil e o v erall t hi s pr o gr a m pr o vi d e s a b e n e fit t o st u d e nt s, s o m e t e a c h er s cr e at e d m or e eff e cti v e c o nt e nt t h a n ot h er s. D e s pit e t hi s fi n di n g, w e di d n ot fi n d e vi d e n c e t h at t h e eff e cti v e n e s s of c o nt e nt r eli a bl y v ari e d b y st u d e nt k n o wl e d g e-l e v el, s u g g e sti n g t h at t h e c o nt e nt i s u nli k el y s uit a bl e f or p er s o n ali zi n g i n str u cti o n b a s e d o n st u d e nt k n o wl e d g e al o n e. T h e s e fi n di n g s ar e pr o mi si n g f or t h e f ut ur e of cr o w d s o ur c e d t ut ori n g a s t h e y h el p pr o vi d e a f o u n d ati o n f or a s s e s si n g t h e q u alit y of cr o w d s o ur c e d c o nt e nt a n d i n v e sti g ati n g c o nt e nt f or o p p ort u niti e s t o p er s o n ali z e st u d e nt s’ e d u c ati o n. 
    more » « less
  5. {"Abstract":["This classified_bed data product represents the radar bed classification shown in <a href="https://doi.org/10.1098/rsta.2014.0297">Young et al., 2016</a>. Values of 0 represent specularity content below 20%; values of 3.3 represent specularity content above 20% and energy 1 microsecond below the bed 15 dB lower than the bed echo, and values of 6.7 represent specularity content above 20% and energy 1 microsecond below the bed 15 dB within than the bed echo. Grids for specularity content and post bed echo are also available. Data is available as COARDS-compliant netCDF-4/HDF5 grids (.grd) and GeoTiffs (.tiff), both in EPSG 3031 (Antarctic Polar Stereographic) projection.\n<p>\n<p>\nData were gridded using <a href="https://docs.generic-mapping-tools.org/6.1/gmt.html"> GMT6.1</a> and the <a href="https://github.com/sakov/nn-c">nnbathy</a> natural neighbor interpolator. Cell size was 1 km, gaussian filter distance was 5 km, and mask radius was 2 km.\n<p>\nBrowse images, with Bedmap3 (Pritchard et al., 2025) surface elevation contours and MEASURES phase derived surface velocities (Mouginot et al. 2019) are available for each dataset.\n\n<p>\n<p>\nAn interpretation of the values in the classified_bed product is that low values are rough bed, intermediate values are isotropic wet bed, and high values are anisotropic wet bed.\n\nVersion 1 includes data from the 2016 paper, including AGASEA over Thwaites Glacier (Holt et al., 2006), ATRS over West Antarctica (Peters et al., 2005), GIMBLE over Marie Byrd Land (Young et al, 2013) and parts of ICECAP over Wilkes Subglacial Basin, Dome C, Highland B and Totten Glacier. (Young et al, 2011, Young et al., 2016). We expect updates to the coverage as part of work funded by the ArΓͺte Glaciers Initiative.\n\n<p>\n<b>References</b>\n<br>\nHolt, J. W., Blankenship, D. D., Morse, D. L., Young, D. A., Peters, M. E., Kempf, S. D., Richter, T. G., Vaughan, D. G., and Corr, H., New boundary conditions for the West Antarctic ice sheet: subglacial topography of the Thwaites and Smith Glacier catchments, 2006, Geophysical Research Letters, 33 (L09502), pp., https://doi.org/10.1029/2005GL025561\n<br>\nMouginot, J., Rignot, E., and Scheuchl, B., Continent-wide, interferometric SAR phase, mapping of Antarctic ice velocity, 2019, Geophysical Research Letters, 46(16), pp.9710-9718, https://doi.org/10.1029/2019GL083826\n<br>\nPeters, M. E., Blankenship, D. D., and Morse, D. L., Analysis techniques for coherent airborne radar sounding: Application to West Antarctic ice streams, 2005 ,Journal of Geophysical Research, 110(B06303), pp.,https://doi.org/10.1029/2004JB003222\n<br>\nPritchard, H. D., and others.,Bedmap3 updated ice bed, surface and thickness gridded datasets for Antarctica,2025,Scientific Data,12(1), pp.414,https://doi.org/10.1038/s41597-025-04672-y\n<br>\nYoung, D. A., D. D. Blankenship, J. S. Greenbaum, E. Quartini, G. L. Muldoon, F. Habbal, L. E. Lindzey, C. A. Greene, E. M. Powell, G. C. Ng, T. G. Richter, G. Echeverry, and S. Kempf, 2024, Geophysical Investigations of Marie Byrd Land Lithospheric Evolution (GIMBLE) Airborne VHF Radar Transects: 2012/2013 and 2014/2015, https://doi.org/10.18738/T8/BMXUHX, Texas Data Repository\n<br>\nYoung, D. A., Wright, A. P., Roberts, J. L., Warner, R. C., Young, N. W., Greenbaum, J. S., Schroeder, D. M., Holt, J. W., Sugden, D. E., Blankenship, D. D., van Ommen, T. D., and Siegert, M. J.,A dynamic early East Antarctic Ice Sheet suggested by ice covered fjord landscapes, 2011, Nature, 474, pp.72-75, https://doi.org/10.1038/nature10114\n<br>\nYoung, D. A., Schroeder, D. M., Blankenship, D. D., Kempf, S. D., and Quartini, E.,The distribution of basal water between Antarctic subglacial lakes from radar sounding,2016,Philosophical Transactions of the Royal Society A, 374 (20140297), pp.1-21, https://doi.org/10.1098/rsta.2014.0297\n\n<p>\n<b>Change Log</b>\n<br>\nChanges from V1: changes to gridding parameters to more closely match the figures from Young 2016; updated metadata gridding description"]} 
    more » « less