Kavli Energy Nanosciences Institute

Berkeley, CA, United States

Kavli Energy Nanosciences Institute

Berkeley, CA, United States
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Diercks C.S.,King Abdulaziz City for Science and Technology | Yaghi O.M.,University of California at Berkeley | Yaghi O.M.,Lawrence Berkeley National Laboratory | Yaghi O.M.,Kavli Energy NanoSciences Institute | Yaghi O.M.,Berkeley Global Science Institute
Science | Year: 2017

Just over a century ago, Lewis published his seminal work on what became known as the covalent bond, which has since occupied a central role in the theory of making organic molecules. With the advent of covalent organic frameworks (COFs), the chemistry of the covalent bond was extended to two- and three-dimensional frameworks. Here, organic molecules are linked by covalent bonds to yield crystalline, porous COFs from light elements (boron, carbon, nitrogen, oxygen, and silicon) that are characterized by high architectural and chemical robustness. This discovery paved the way for carrying out chemistry on frameworks without losing their porosity or crystallinity, and in turn achieving designed properties in materials. The recent union of the covalent and the mechanical bond in the COF provides the opportunity for making woven structures that incorporate flexibility and dynamics into frameworks.


News Article | November 9, 2016
Site: www.sciencedaily.com

Solar cells made from an inexpensive and increasingly popular material called perovskite can more efficiently turn sunlight into electricity using a new technique to sandwich two types of perovskite into a single photovoltaic cell. Perovskite solar cells are made of a mix of organic molecules and inorganic elements that together capture light and convert it into electricity, just like today's more common silicon-based solar cells. Perovskite photovoltaic devices, however, can be made more easily and cheaply than silicon and on a flexible rather than rigid substrate. The first perovskite solar cells could go on the market next year, and some have been reported to capture 20 percent of the sun's energy. In a paper appearing online in advance of publication in the journal Nature Materials, University of California, Berkeley, and Lawrence Berkeley National Laboratory scientists report a new design that already achieves an average steady-state efficiency of 18.4 percent, with a high of 21.7 percent and a peak efficiency of 26 percent. "We have set the record now for different parameters of perovskite solar cells, including the efficiency," said senior author Alex Zettl, a UC Berkeley professor of physics, senior faculty member at Berkeley Lab and member of the Kavli Energy Nanosciences Institute. "The efficiency is higher than any other perovskite cell -- 21.7 percent -- which is a phenomenal number, considering we are at the beginning of optimizing this." "This has a great potential to be the cheapest photovoltaic on the market, plugging into any home solar system," said Onur Ergen, the lead author of the paper and a UC Berkeley physics graduate student. The efficiency is also better than the 10-20 percent efficiency of polycrystalline silicon solar cells used to power most electronic devices and homes. Even the purest silicon solar cells, which are extremely expensive to produce, topped out at about 25 percent efficiency more than a decade ago. The achievement comes thanks to a new way to combine two perovskite solar cell materials -- each tuned to absorb a different wavelength or color of sunlight -- into one "graded bandgap" solar cell that absorbs nearly the entire spectrum of visible light. Previous attempts to merge two perovskite materials have failed because the materials degrade one another's electronic performance. "This is realizing a graded bandgap solar cell in a relatively easy-to-control and easy-to-manipulate system," Zettl said. "The nice thing about this is that it combines two very valuable features -- the graded bandgap, a known approach, with perovskite, a relatively new but known material with surprisingly high efficiencies -- to get the best of both worlds." Materials like silicon and perovskite are semiconductors, which means they conduct electricity only if the electrons can absorb enough energy -- from a photon of light, for example -- to kick them over a forbidden energy gap or bandgap. These materials preferentially absorb light at specific energies or wavelengths -- the bandgap energy -- but inefficiently at other wavelengths. "In this case, we are swiping the entire solar spectrum from infrared through the entire visible spectrum," Ergen said. "Our theoretical efficiency calculations should be much, much higher and easier to reach than for single-bandgap solar cells because we can maximize coverage of the solar spectrum." The key to mating the two materials into a tandem solar cell is a single-atom thick layer of hexagonal boron nitride, which looks like a layer of chicken wire separating the perovskite layers from one other. In this case, the perovskite materials are made of the organic molecules methyl and ammonia, but one contains the metals tin and iodine, while the other contains lead and iodine doped with bromine. The former is tuned to preferentially absorb light with an energy of 1 electron volt (eV) -- infrared, or heat energy -- while the latter absorbs photons of energy 2 eV, or an amber color. The monolayer of boron nitride allows the two perovskite materials to work together and make electricity from light across the whole range of colors between 1 and 2 eV. The perovskite/boron nitride sandwich is placed atop a lightweight aerogel of graphene that promotes the growth of finer-grained perovskite crystals, serves as a moisture barrier and helps stabilize charge transport though the solar cell, Zettl said. Moisture makes perovskite fall apart. The whole thing is capped at the bottom with a gold electrode and at the top by a gallium nitride layer that collects the electrons that are generated within the cell. The active layer of the thin-film solar cell is about 400 nanometers thick. "Our architecture is a bit like building a quality automobile roadway," Zettl said. "The graphene aerogel acts like the firm, crushed rock bottom layer or foundation, the two perovskite layers are like finer gravel and sand layers deposited on top of that, with the hexagonal boron nitride layer acting like a thin-sheet membrane between the gravel and sand that keeps the sand from diffusing into or mixing too much with the finer gravel. The gallium nitride layer serves as the top asphalt layer." It is possible to add even more layers of perovskite separated by hexagonal boron nitride, though this may not be necessary, given the broad-spectrum efficiency they've already obtained, the researchers said. "People have had this idea of easy-to-make, roll-to-roll photovoltaics, where you pull plastic off a roll, spray on the solar material, and roll it back up," Zettl said. "With this new material, we are in the regime of roll-to-roll mass production; it's really almost like spray painting."


News Article | November 8, 2016
Site: www.eurekalert.org

Solar cells made from an inexpensive and increasingly popular material called perovskite can more efficiently turn sunlight into electricity using a new technique to sandwich two types of perovskite into a single photovoltaic cell. Perovskite solar cells are made of a mix of organic molecules and inorganic elements that together capture light and convert it into electricity, just like today's more common silicon-based solar cells. Perovskite photovoltaic devices, however, can be made more easily and cheaply than silicon and on a flexible rather than rigid substrate. The first perovskite solar cells could go on the market next year, and some have been reported to capture 20 percent of the sun's energy. In a paper appearing online today in advance of publication in the journal Nature Materials, University of California, Berkeley, and Lawrence Berkeley National Laboratory scientists report a new design that already achieves an average steady-state efficiency of 18.4 percent, with a high of 21.7 percent and a peak efficiency of 26 percent. "We have set the record now for different parameters of perovskite solar cells, including the efficiency," said senior author Alex Zettl, a UC Berkeley professor of physics, senior faculty member at Berkeley Lab and member of the Kavli Energy Nanosciences Institute. "The efficiency is higher than any other perovskite cell - 21.7 percent - which is a phenomenal number, considering we are at the beginning of optimizing this." "This has a great potential to be the cheapest photovoltaic on the market, plugging into any home solar system," said Onur Ergen, the lead author of the paper and a UC Berkeley physics graduate student. The efficiency is also better than the 10-20 percent efficiency of polycrystalline silicon solar cells used to power most electronic devices and homes. Even the purest silicon solar cells, which are extremely expensive to produce, topped out at about 25 percent efficiency more than a decade ago. The achievement comes thanks to a new way to combine two perovskite solar cell materials - each tuned to absorb a different wavelength or color of sunlight - into one "graded bandgap" solar cell that absorbs nearly the entire spectrum of visible light. Previous attempts to merge two perovskite materials have failed because the materials degrade one another's electronic performance. "This is realizing a graded bandgap solar cell in a relatively easy-to-control and easy-to-manipulate system," Zettl said. "The nice thing about this is that it combines two very valuable features - the graded bandgap, a known approach, with perovskite, a relatively new but known material with surprisingly high efficiencies - to get the best of both worlds." Materials like silicon and perovskite are semiconductors, which means they conduct electricity only if the electrons can absorb enough energy - from a photon of light, for example - to kick them over a forbidden energy gap or bandgap. These materials preferentially absorb light at specific energies or wavelengths - the bandgap energy - but inefficiently at other wavelengths. "In this case, we are swiping the entire solar spectrum from infrared through the entire visible spectrum," Ergen said. "Our theoretical efficiency calculations should be much, much higher and easier to reach than for single-bandgap solar cells because we can maximize coverage of the solar spectrum." The key to mating the two materials into a tandem solar cell is a single-atom thick layer of hexagonal boron nitride, which looks like a layer of chicken wire separating the perovskite layers from one other. In this case, the perovskite materials are made of the organic molecules methyl and ammonia, but one contains the metals tin and iodine, while the other contains lead and iodine doped with bromine. The former is tuned to preferentially absorb light with an energy of 1 electron volt (eV) - infrared, or heat energy - while the latter absorbs photons of energy 2 eV, or an amber color. The monolayer of boron nitride allows the two perovskite materials to work together and make electricity from light across the whole range of colors between 1 and 2 eV. The perovskite/boron nitride sandwich is placed atop a lightweight aerogel of graphene that promotes the growth of finer-grained perovskite crystals, serves as a moisture barrier and helps stabilize charge transport though the solar cell, Zettl said. Moisture makes perovskite fall apart. The whole thing is capped at the bottom with a gold electrode and at the top by a gallium nitride layer that collects the electrons that are generated within the cell. The active layer of the thin-film solar cell is about 400 nanometers thick. "Our architecture is a bit like building a quality automobile roadway," Zettl said. "The graphene aerogel acts like the firm, crushed rock bottom layer or foundation, the two perovskite layers are like finer gravel and sand layers deposited on top of that, with the hexagonal boron nitride layer acting like a thin-sheet membrane between the gravel and sand that keeps the sand from diffusing into or mixing too much with the finer gravel. The gallium nitride layer serves as the top asphalt layer." It is possible to add even more layers of perovskite separated by hexagonal boron nitride, though this may not be necessary, given the broad-spectrum efficiency they've already obtained, the researchers said. "People have had this idea of easy-to-make, roll-to-roll photovoltaics, where you pull plastic off a roll, spray on the solar material, and roll it back up," Zettl said. "With this new material, we are in the regime of roll-to-roll mass production; it's really almost like spray painting." Co-authors are S. Matt Gilbert, Thang Pham, Sally Turner Mark and Tian Zhi Tan of UC Berkeley and Marcus Worsley of Lawrence Livermore National Laboratory, who produced the graphene aerogel. The work was supported by the U.S. Department of Energy, the National Science Foundation (1542741) and the Office of Naval Research.


News Article | November 15, 2016
Site: www.materialstoday.com

Perovskite solar cells are made from a mix of organic molecules and inorganic elements that together capture light and convert it to electricity, just like today's more common silicon-based solar cells. Perovskite photovoltaic devices, however, can be made more easily and cheaply than silicon and on a flexible rather than rigid substrate. The first perovskite solar cells could go on the market next year, and some can reportedly capture 20% of the sun's energy. In a paper in Nature Materials, scientists from the University of California, Berkeley, and Lawrence Berkeley National Laboratory report a new design that sandwiches two types of perovskite into a single photovoltaic cell. Using this design, they have already achieved an average steady-state efficiency of 18.4%, with a high of 21.7% and a peak efficiency of 26%. "We have set the record now for different parameters of perovskite solar cells, including the efficiency," said senior author Alex Zettl, a UC Berkeley professor of physics, senior faculty member at Berkeley Lab and member of the Kavli Energy Nanosciences Institute. "The efficiency is higher than any other perovskite cell – 21.7% – which is a phenomenal number, considering we are at the beginning of optimizing this." "This has a great potential to be the cheapest photovoltaic on the market, plugging into any home solar system," said Onur Ergen, the lead author of the paper and a UC Berkeley physics graduate student. The efficiency of this new perovskite cell is also better than the 10–20% efficiency of the polycrystalline silicon solar cells used to power most electronic devices and homes. Even the purest silicon solar cells, which are extremely expensive to produce, topped out at about 25% efficiency more than a decade ago. The record efficiency was achieved by combining two perovskite solar cell materials – each tuned to absorb a different wavelength of sunlight – into one ‘graded bandgap’ solar cell that absorbs nearly the entire spectrum of visible light. Previous attempts to merge two perovskite materials have failed because the materials degrade one another's electronic performance. "This is realizing a graded bandgap solar cell in a relatively easy-to-control and easy-to-manipulate system," Zettl said. "The nice thing about this is that it combines two very valuable features – the graded bandgap, a known approach, with perovskite, a relatively new but known material with surprisingly high efficiencies – to get the best of both worlds." Materials like silicon and perovskite are semiconductors, which means they conduct electricity only if the electrons can absorb enough energy – from a photon of light, for example – to kick them over a forbidden energy gap, or bandgap. These materials preferentially absorb light at specific energies or wavelengths – the bandgap energy – but absorb other wavelengths much less efficiently. "In this case, we are swiping the entire solar spectrum from infrared through the entire visible spectrum," Ergen said. "Our theoretical efficiency calculations should be much, much higher and easier to reach than for single-bandgap solar cells because we can maximize coverage of the solar spectrum." The key to combining the two perovskite materials into a tandem solar cell is a single-atom thick layer of hexagonal boron nitride, which looks like a layer of chicken wire separating the perovskite layers from one other. In this case, the perovskite materials are made of the organic molecules methyl and ammonia, but one also contains the metals tin and iodine, while the other contains lead and iodine doped with bromine. The former is tuned to preferentially absorb light with an energy of 1 electron volt (eV) – infrared, or heat energy – while the latter absorbs photons with an energy of 2 eV – an amber color. The monolayer of boron nitride thus allows these two perovskite materials to work together to generate electricity from light with energies ranging between 1eV and 2eV. This perovskite/boron nitride sandwich is placed atop a lightweight aerogel of graphene that promotes the growth of finer-grained perovskite crystals, serves as a moisture barrier and helps to stabilize charge transport though the solar cell, Zettl said. Moisture makes perovskite fall apart. The whole thing is capped at the bottom with a gold electrode and at the top by a gallium nitride layer that collects the electrons generated within the cell. The active layer of this thin-film solar cell is only around 400nm thick. "Our architecture is a bit like building a quality automobile roadway," explained Zettl. "The graphene aerogel acts like the firm, crushed rock bottom layer or foundation, the two perovskite layers are like finer gravel and sand layers deposited on top of that, with the hexagonal boron nitride layer acting like a thin-sheet membrane between the gravel and sand that keeps the sand from diffusing into or mixing too much with the finer gravel. The gallium nitride layer serves as the top asphalt layer." It should also be possible to add even more layers of perovskite separated by hexagonal boron nitride, say the researchers, though this may not be necessary given the broad-spectrum efficiency they've already obtained. "People have had this idea of easy-to-make, roll-to-roll photovoltaics, where you pull plastic off a roll, spray on the solar material and roll it back up," Zettl said. "With this new material, we are in the regime of roll-to-roll mass production; it's really almost like spray painting." This story is adapted from material from the University of California, Berkeley, with editorial changes made by Materials Today. The views expressed in this article do not necessarily represent those of Elsevier. Link to original source.


News Article | November 8, 2016
Site: phys.org

Perovskite solar cells are made of a mix of organic molecules and inorganic elements that together capture light and convert it into electricity, just like today's more common silicon-based solar cells. Perovskite photovoltaic devices, however, can be made more easily and cheaply than silicon and on a flexible rather than rigid substrate. The first perovskite solar cells could go on the market next year, and some have been reported to capture 20 percent of the sun's energy. In a paper appearing online today in advance of publication in the journal Nature Materials, University of California, Berkeley, and Lawrence Berkeley National Laboratory scientists report a new design that already achieves an average steady-state efficiency of 18.4 percent, with a high of 21.7 percent and a peak efficiency of 26 percent. "We have set the record now for different parameters of perovskite solar cells, including the efficiency," said senior author Alex Zettl, a UC Berkeley professor of physics, senior faculty member at Berkeley Lab and member of the Kavli Energy Nanosciences Institute. "The efficiency is higher than any other perovskite cell - 21.7 percent - which is a phenomenal number, considering we are at the beginning of optimizing this." "This has a great potential to be the cheapest photovoltaic on the market, plugging into any home solar system," said Onur Ergen, the lead author of the paper and a UC Berkeley physics graduate student. The efficiency is also better than the 10-20 percent efficiency of polycrystalline silicon solar cells used to power most electronic devices and homes. Even the purest silicon solar cells, which are extremely expensive to produce, topped out at about 25 percent efficiency more than a decade ago. The achievement comes thanks to a new way to combine two perovskite solar cell materials - each tuned to absorb a different wavelength or color of sunlight - into one "graded bandgap" solar cell that absorbs nearly the entire spectrum of visible light. Previous attempts to merge two perovskite materials have failed because the materials degrade one another's electronic performance. "This is realizing a graded bandgap solar cell in a relatively easy-to-control and easy-to-manipulate system," Zettl said. "The nice thing about this is that it combines two very valuable features - the graded bandgap, a known approach, with perovskite, a relatively new but known material with surprisingly high efficiencies - to get the best of both worlds." Materials like silicon and perovskite are semiconductors, which means they conduct electricity only if the electrons can absorb enough energy - from a photon of light, for example - to kick them over a forbidden energy gap or bandgap. These materials preferentially absorb light at specific energies or wavelengths - the bandgap energy - but inefficiently at other wavelengths. "In this case, we are swiping the entire solar spectrum from infrared through the entire visible spectrum," Ergen said. "Our theoretical efficiency calculations should be much, much higher and easier to reach than for single-bandgap solar cells because we can maximize coverage of the solar spectrum." The key to mating the two materials into a tandem solar cell is a single-atom thick layer of hexagonal boron nitride, which looks like a layer of chicken wire separating the perovskite layers from one other. In this case, the perovskite materials are made of the organic molecules methyl and ammonia, but one contains the metals tin and iodine, while the other contains lead and iodine doped with bromine. The former is tuned to preferentially absorb light with an energy of 1 electron volt (eV) - infrared, or heat energy - while the latter absorbs photons of energy 2 eV, or an amber color. The monolayer of boron nitride allows the two perovskite materials to work together and make electricity from light across the whole range of colors between 1 and 2 eV. The perovskite/boron nitride sandwich is placed atop a lightweight aerogel of graphene that promotes the growth of finer-grained perovskite crystals, serves as a moisture barrier and helps stabilize charge transport though the solar cell, Zettl said. Moisture makes perovskite fall apart. The whole thing is capped at the bottom with a gold electrode and at the top by a gallium nitride layer that collects the electrons that are generated within the cell. The active layer of the thin-film solar cell is about 400 nanometers thick. "Our architecture is a bit like building a quality automobile roadway," Zettl said. "The graphene aerogel acts like the firm, crushed rock bottom layer or foundation, the two perovskite layers are like finer gravel and sand layers deposited on top of that, with the hexagonal boron nitride layer acting like a thin-sheet membrane between the gravel and sand that keeps the sand from diffusing into or mixing too much with the finer gravel. The gallium nitride layer serves as the top asphalt layer." It is possible to add even more layers of perovskite separated by hexagonal boron nitride, though this may not be necessary, given the broad-spectrum efficiency they've already obtained, the researchers said. "People have had this idea of easy-to-make, roll-to-roll photovoltaics, where you pull plastic off a roll, spray on the solar material, and roll it back up," Zettl said. "With this new material, we are in the regime of roll-to-roll mass production; it's really almost like spray painting."


Yan S.,University of California at Berkeley | Wen J.-D.,National Taiwan University | Bustamante C.,University of California at Berkeley | Bustamante C.,Howard Hughes Medical Institute | And 2 more authors.
Cell | Year: 2015

Programmed ribosomal frameshifting produces alternative proteins from a single transcript. -1 frameshifting occurs on Escherichia coli's dnaX mRNA containing a slippery sequence AAAAAAG and peripheral mRNA structural barriers. Here, we reveal hidden aspects of the frameshifting process, including its exact location on the mRNA and its timing within the translation cycle. Mass spectrometry of translated products shows that ribosomes enter the -1 frame from not one specific codon but various codons along the slippery sequence and slip by not just -1 but also -4 or +2 nucleotides. Single-ribosome translation trajectories detect distinctive codon-scale fluctuations in ribosome-mRNA displacement across the slippery sequence, representing multiple ribosomal translocation attempts during frameshifting. Flanking mRNA structural barriers mechanically stimulate the ribosome to undergo back-and-forth translocation excursions, broadly exploring reading frames. Both experiments reveal aborted translation around mutant slippery sequences, indicating that subsequent fidelity checks on newly adopted codon position base pairings lead to either resumed translation or early termination. © 2015 Elsevier Inc.


Sakimoto K.K.,University of California at Berkeley | Sakimoto K.K.,Lawrence Berkeley National Laboratory | Wong A.B.,University of California at Berkeley | Wong A.B.,Lawrence Berkeley National Laboratory | And 3 more authors.
Science | Year: 2016

Improving natural photosynthesis can enable the sustainable production of chemicals. However, neither purely artificial nor purely biological approaches seem poised to realize the potential of solar-to-chemical synthesis.We developed a hybrid approach, whereby we combined the highly efficient light harvesting of inorganic semiconductors with the high specificity, low cost, and self-replication and -repair of biocatalysts.We induced the self-photosensitization of a nonphotosynthetic bacterium, Moorella thermoacetica, with cadmium sulfide nanoparticles, enabling the photosynthesis of acetic acid from carbon dioxide. Biologically precipitated cadmium sulfide nanoparticles served as the light harvester to sustain cellular metabolism.This self-augmented biological system selectively produced acetic acid continuously over several days of light-dark cycles at relatively high quantum yields, demonstrating a self-replicating route toward solar-to-chemical carbon dioxide reduction.


Kim D.,University of California at Berkeley | Sakimoto K.K.,University of California at Berkeley | Hong D.,University of California at Berkeley | Yang P.,University of California at Berkeley | Yang P.,Kavli Energy Nanosciences Institute
Angewandte Chemie - International Edition | Year: 2015

The apparent incongruity between the increasing consumption of fuels and chemicals and the finite amount of resources has led us to seek means to maintain the sustainability of our society. Artificial photosynthesis, which utilizes sunlight to create high-value chemicals from abundant resources, is considered as the most promising and viable method. This Minireview describes the progress and challenges in the field of artificial photosynthesis in terms of its key components: developments in photoelectrochemical water splitting and recent progress in electrochemical CO2 reduction. Advances in catalysis, concerning the use of renewable hydrogen as a feedstock for major chemical production, are outlined to shed light on the ultimate role of artificial photosynthesis in achieving sustainable chemistry. © 2015 Wiley-VCH Verlag GmbH & Co. KGaA.


Wong C.Y.,University of California at Berkeley | Cotts B.L.,University of California at Berkeley | Wu H.,University of California at Berkeley | Ginsberg N.S.,University of California at Berkeley | And 2 more authors.
Nature Communications | Year: 2015

Large-scale organic electronics manufacturing requires solution processing. For small-molecule organic semiconductors, solution processing results in crystalline domains with high charge mobility, but the interfaces between these domains impede charge transport, degrading device performance. Although understanding these interfaces is essential to improve device performance, their intermolecular and electronic structure is unknown: they are smaller than the diffraction limit, are hidden from surface probe techniques, and their nanoscale heterogeneity is not typically resolved using X-ray methods. Here we use transient absorption microscopy to isolate a unique signature of a hidden interface in a TIPS-pentacene thin film, exposing its exciton dynamics and intermolecular structure. Surprisingly, instead of finding an abrupt grain boundary, we reveal that the interface can be composed of nanoscale crystallites interleaved by a web of interfaces that compound decreases in charge mobility. Our novel approach provides critical missing information on interface morphology necessary to correlate solution-processing methods to optimal device performance. © 2015 Macmillan Publishers Limited.


Kim D.,University of California at Berkeley | Resasco J.,University of California at Berkeley | Yu Y.,University of California at Berkeley | Asiri A.M.,King Abdulaziz University | And 2 more authors.
Nature Communications | Year: 2014

Highly efficient and selective electrochemical reduction of carbon dioxide represents one of the biggest scientific challenges in artificial photosynthesis, where carbon dioxide and water are converted into chemical fuels from solar energy. However, our fundamental understanding of the reaction is still limited and we do not have the capability to design an outstanding catalyst with great activity and selectivity a priori. Here we assemble uniform gold-copper bimetallic nanoparticles with different compositions into ordered monolayers, which serve as a well-defined platform to understand their fundamental catalytic activity in carbon dioxide reduction. We find that two important factors related to intermediate binding, the electronic effect and the geometric effect, dictate the activity of gold-copper bimetallic nanoparticles. These nanoparticle monolayers also show great mass activities, outperforming conventional carbon dioxide reduction catalysts. The insights gained through this study may serve as a foundation for designing better carbon dioxide electrochemical reduction catalysts. © 2014 Macmillan Publishers Limited. All rights reserved.

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