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1.
J Chem Phys ; 153(4): 044126, 2020 Jul 28.
Artigo em Inglês | MEDLINE | ID: mdl-32752722

RESUMO

Elementary steps and intermediate species of linearly structured biomass compounds are studied. Specifically, possible intermediates and elementary reactions of 15 key biomass compounds and 33 small molecules are obtained from a recursive bond-breaking algorithm. These are used as inputs to the unsupervised Mol2Vec algorithm to generate vector representations of all intermediates and elementary reactions. The vector descriptors are used to identify sub-classes of elementary steps, and linear discriminant analysis is used to accurately identify the reaction type and reduce the dimension of the vectors. The resulting descriptors are applied to predict gas-phase reaction energies using linear regression with accuracies that exceed the commonly employed group additivity approach. They are also applied to quantitatively assess model compound similarity, and the results are consistent with chemical intuition. This workflow for creating vector representations of complex molecular systems requires no input from electronic structure calculations, and it is expected to be applicable to other similar systems where vector representations are needed.

2.
J Am Chem Soc ; 140(45): 15157-15160, 2018 11 14.
Artigo em Inglês | MEDLINE | ID: mdl-30372055

RESUMO

Photo-catalytic fixation of nitrogen by titania catalysts at ambient conditions has been reported for decades, yet the active site capable of adsorbing an inert N2 molecule at ambient pressure and the mechanism of dissociating the strong dinitrogen triple bond at room temperature remain unknown. In this work in situ near-ambient-pressure X-ray photo-electron spectroscopy and density functional theory calculations are used to probe the active state of the rutile (110) surface. The experimental results indicate that photon-driven interaction of N2 and TiO2 is observed only if adventitious surface carbon is present, and computational results show a remarkably strong interaction between N2 and carbon substitution (C*) sites that act as surface-bound carbon radicals. A carbon-assisted nitrogen reduction mechanism is proposed and shown to be thermodynamically feasible. The findings provide a molecular-scale explanation for the long-standing mystery of photo-catalytic nitrogen fixation on titania. The results suggest that controlling and characterizing carbon-based active sites may provide a route to engineering more efficient photo(electro)-catalysts and improving experimental reproducibility.

3.
Angew Chem Int Ed Engl ; 57(46): 15045-15050, 2018 Nov 12.
Artigo em Inglês | MEDLINE | ID: mdl-30134041

RESUMO

Methanol is a major fuel and chemical feedstock currently produced from syngas, a CO/CO2 /H2 mixture. Herein we identify formate binding strength as a key parameter limiting the activity and stability of known catalysts for methanol synthesis in the presence of CO2 . We present a molybdenum phosphide catalyst for CO and CO2 reduction to methanol, which through a weaker interaction with formate, can improve the activity and stability of methanol synthesis catalysts in a wide range of CO/CO2 /H2 feeds.

4.
Nat Commun ; 8: 14621, 2017 03 06.
Artigo em Inglês | MEDLINE | ID: mdl-28262694

RESUMO

Surface reaction networks involving hydrocarbons exhibit enormous complexity with thousands of species and reactions for all but the very simplest of chemistries. We present a framework for optimization under uncertainty for heterogeneous catalysis reaction networks using surrogate models that are trained on the fly. The surrogate model is constructed by teaching a Gaussian process adsorption energies based on group additivity fingerprints, combined with transition-state scaling relations and a simple classifier for determining the rate-limiting step. The surrogate model is iteratively used to predict the most important reaction step to be calculated explicitly with computationally demanding electronic structure theory. Applying these methods to the reaction of syngas on rhodium(111), we identify the most likely reaction mechanism. Propagating uncertainty throughout this process yields the likelihood that the final mechanism is complete given measurements on only a subset of the entire network and uncertainty in the underlying density functional theory calculations.

5.
J Am Chem Soc ; 138(11): 3705-14, 2016 Mar 23.
Artigo em Inglês | MEDLINE | ID: mdl-26958997

RESUMO

Synthesis gas (CO + H2) conversion is a promising route to converting coal, natural gas, or biomass into synthetic liquid fuels. Rhodium has long been studied as it is the only elemental catalyst that has demonstrated selectivity to ethanol and other C2+ oxygenates. However, the fundamentals of syngas conversion over rhodium are still debated. In this work a microkinetic model is developed for conversion of CO and H2 into methane, ethanol, and acetaldehyde on the Rh (211) and (111) surfaces, chosen to describe steps and close-packed facets on catalyst particles. The model is based on DFT calculations using the BEEF-vdW functional. The mean-field kinetic model includes lateral adsorbate-adsorbate interactions, and the BEEF-vdW error estimation ensemble is used to propagate error from the DFT calculations to the predicted rates. The model shows the Rh(211) surface to be ∼6 orders of magnitude more active than the Rh(111) surface, but highly selective toward methane, while the Rh(111) surface is intrinsically selective toward acetaldehyde. A variety of Rh/SiO2 catalysts are synthesized, tested for catalytic oxygenate production, and characterized using TEM. The experimental results indicate that the Rh(111) surface is intrinsically selective toward acetaldehyde, and a strong inverse correlation between catalytic activity and oxygenate selectivity is observed. Furthermore, iron impurities are shown to play a key role in modulating the selectivity of Rh/SiO2 catalysts toward ethanol. The experimental observations are consistent with the structure-sensitivity predicted from theory. This work provides an improved atomic-scale understanding and new insight into the mechanism, active site, and intrinsic selectivity of syngas conversion over rhodium catalysts and may also guide rational design of alloy catalysts made from more abundant elements.

6.
Angew Chem Int Ed Engl ; 55(17): 5210-4, 2016 Apr 18.
Artigo em Inglês | MEDLINE | ID: mdl-27005967

RESUMO

Bifunctional coupling of two different catalytic site types has often been invoked to explain experimentally observed enhanced catalytic activities. We scrutinize such claims with generic scaling-relation-based microkinetic models that allow exploration of the theoretical limits for such a bifunctional gain for several model reactions. For sites at transition-metal surfaces, the universality of the scaling relations between adsorption energies largely prevents any improvements through bifunctionality. Only the consideration of systems that involve the combination of different materials, such as metal particles on oxide supports, offers hope for significant bifunctional gains.

7.
Science ; 345(6193): 197-200, 2014 Jul 11.
Artigo em Inglês | MEDLINE | ID: mdl-25013071

RESUMO

We introduce a general method for estimating the uncertainty in calculated materials properties based on density functional theory calculations. We illustrate the approach for a calculation of the catalytic rate of ammonia synthesis over a range of transition-metal catalysts. The correlation between errors in density functional theory calculations is shown to play an important role in reducing the predicted error on calculated rates. Uncertainties depend strongly on reaction conditions and catalyst material, and the relative rates between different catalysts are considerably better described than the absolute rates. We introduce an approach for incorporating uncertainty when searching for improved catalysts by evaluating the probability that a given catalyst is better than a known standard.

8.
Opt Express ; 18 Suppl 3: A272-85, 2010 Sep 13.
Artigo em Inglês | MEDLINE | ID: mdl-21165057

RESUMO

Large solar panels were constructed from polymer solar cell modules prepared using full roll-to-roll (R2R) manufacture based on the previously published ProcessOne. The individual flexible polymer solar modules comprising multiple serially connected single cell stripes were joined electrically and laminated between a 4 mm tempered glass window and black Tetlar foil using two sheets of 0.5 mm thick ethylene vinyl acetate (EVA). The panels produced up to 8 W with solar irradiance of ~960 Wm⁻², and had outer dimensions of 1 m x 1.7 m with active areas up to 9180 cm². Panels were mounted on a tracking station and their output was grid connected between testing. Several generations of polymer solar cells and panel constructions were tested in this context to optimize the production of polymer solar panels. Cells lacking a R2R barrier layer were found to degrade due to diffusion of oxygen after less than a month, while R2R encapsulated cells showed around 50% degradation after 6 months but suffered from poor performance due to de-lamination during panel production. A third generation of panels with various barrier layers was produced to optimize the choice of barrier foil and it was found that the inclusion of a thin protective foil between the cell and the barrier foil is critical. The findings provide a preliminary foundation for the production and optimization of large-area polymer solar panels and also enabled a cost analysis of solar panels based on polymer solar cells.

9.
ACS Appl Mater Interfaces ; 2(10): 2819-27, 2010 Oct.
Artigo em Inglês | MEDLINE | ID: mdl-20879717

RESUMO

We present a technique that enables the probing of the entire parameter space for each parameter with good statistics through a simple roll-to-roll processing method where gradients of donor, acceptor, and solvent are applied by differentially pumped slot-die coating. We thus demonstrate how the optimum donor-acceptor ratio and device film thickness can be determined with improved accuracy by varying the composition in small steps. We give as an example P3HT-PCBM devices and vary the composition between P3HT and PCBM in steps of 0.5-1% giving 100-200 individual solar cells. The coating experiment itself takes less than 4-8 min and requires 15-30 mg each of donor and acceptor material. The optimum donor-acceptor composition of P3HT and PCBM was found to be a broad maximum centered on a 1:1 ratio. We demonstrate how the optimal thickness of the active layer can be found by the same method and materials usage by variation of the layer thickness in small steps of 1.5-4 nm. Contrary to expectation we did not find oscillatory variation of the device performance with device thickness because of optical interference. We ascribe this to the nature of the solar cell type explored in this example that employs nonreflective or semitransparent printed electrodes. We further found that very thick active layers on the order of 1 µm can be prepared without loss in performance and estimate the active layer thickness could easily approach 4-5 µm while maintaining photovoltaic properties.

10.
Chemistry ; 16(38): 11543-8, 2010 Oct 11.
Artigo em Inglês | MEDLINE | ID: mdl-20827708

RESUMO

Protective coating: Carbon-SnO(2) core-sheath composite nanofibers are synthesized through the creative combination of electrospinning and electrodeposition processes (see figure). They display excellent electrochemical performance when directly used as binder-free anodes for rechargeable lithium ion batteries.

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