Edward H. Sargent

The fundamental properties and ultimate performance limits of organolead trihalide MAPbX3 (MA = CH3NH3(+); X = Br(-) or I(-)) perovskites remain obscured by extensive disorder in polycrystalline MAPbX3 films. We report an antisolvent vapor-assisted crystallization approach that enables us to create sizable crack-free MAPbX3 single crystals with volumes exceeding 100 cubic millimeters. These large single crystals enabled a detailed characterization of their optical and charge transport characteristics. We observed exceptionally low trap-state densities on the order of 10(9) to 10(10) per cubic centimeter in MAPbX3 single crystals (comparable to the best photovoltaic-quality silicon) and charge carrier diffusion lengths exceeding 10 micrometers. These results were validated with density functional theory calculations.

BACKGROUND As the world continues to transition toward carbon emissions–free energy technologies, there remains a need to also reduce the carbon emissions of the chemical production industry. Today many of the world’s chemicals are produced from fossil fuel–derived feedstocks. Electrochemical conversion of carbon dioxide (CO 2 ) into chemical feedstocks offers a way to turn waste emissions into valuable products, closing the carbon loop. When coupled to renewable sources of electricity, these products can be made with a net negative carbon emissions footprint, helping to sequester CO 2 into usable goods. Research and development into electrocatalytic materials for CO 2 reduction has intensified in recent years, with advances in selectivity, efficiency, and reaction rate progressing toward practical implementation. A variety of chemical products can be made from CO 2 , such as alcohols, oxygenates, synthesis gas (syngas), and olefins—staples in the global chemical industry. Because these products are produced at substantial scale, a switch to renewably powered production could result in a substantial carbon emissions reduction impact. The advancement of electrochemical technology to convert electrons generated from renewable power into stable chemical form also represents one avenue to long-term (e.g., seasonal) storage of energy. ADVANCES The science of electrocatalytic CO 2 reduction continues to progress, with priority given to the need to pinpoint more accurately the targets for practical application, the economics of chemical products, and barriers to market entry. It will be important to scale CO 2 electrolyzers and increase the stability of these catalysts to thousands of hours of continuous operation. Product separation and efficient recycling of CO 2 and electrolyte also need to be managed. The petrochemical industry operates at a massive scale with a complicated global supply chain and heavy capital costs. Commodity chemical markets are difficult to penetrate and are priced on feedstock, which is currently inexpensive as a result of the shale gas boom. CO 2 capture costs from the flue or direct air and product separation from unreacted CO 2 are also important to consider. Assuming that the advancement of electrocatalytic technologies continues apace, what will it take to disrupt the chemical production sector, and what will society gain by doing so? This review presents a technoeconomic and carbon emissions assessment of CO 2 products such as ethylene, ethanol, and carbon monoxide, offering target figures of merit for practical application. The price of electricity is by far the largest cost driver. Electrochemical production costs begin to match those of traditional fossil fuel–derived processes when electricity prices fall below 4 cents per kWh and energy conversion efficiencies reach at least 60%. When powered by renewable electricity, these products can be made with a net negative carbon emissions footprint. A comparative analysis of electrocatalytic, biocatalytic, and fossil fuel–derived chemical production shows that electrocatalytic production has the potential to yield the greatest reduction in carbon emissions, provided that a steady supply of clean electricity is available. Additionally, opportunities exist to combine electrochemical conversion of CO 2 with a range of other thermo- and biocatalytic processes to slowly electrify the existing petrochemical supply chain and further upgrade CO 2 into more useful chemicals. Technical challenges such as operating lifetime, energy efficiency, and product separation are discussed. Supply chain management of products and entrenched industrial petrochemical competition are also considered. OUTLOOK There exists increasingly widespread recognition of the need to transition to carbon emissions–free means of chemical production. CO 2 pricing mechanisms are being developed and are seeing increased governmental support. The nascent carbon utilization economy is gaining traction, with startup companies, global prizes, and industrial research efforts all pursuing new carbon conversion technologies. Recent advances in electrochemical CO 2 reduction through the use of gas diffusion electrodes are pushing current densities and selectivities into a realm of industrial use. Despite this progress, there remain technical challenges that must be overcome for commercial application. Additionally, market barriers and cost economics will ultimately decide whether this technology experiences widespread implementation. Electrochemical CO 2 conversion. Reduction of CO 2 using renewably sourced electricity could transform waste CO 2 emissions into commodity chemical feedstocks or fuels.

A very basic pathway from CO 2 to ethylene Ethylene is an important commodity chemical for plastics. It is considered a tractable target for synthesizing renewably from carbon dioxide (CO 2 ). The challenge is that the performance of the copper electrocatalysts used for this conversion under the required basic reaction conditions suffers from the competing reaction of CO 2 with the base to form bicarbonate. Dinh et al. designed an electrode that tolerates the base by optimizing CO 2 diffusion to the catalytic sites (see the Perspective by Ager and Lapkin). This catalyst design delivers 70% efficiency for 150 hours. Science , this issue p. 783 ; see also p. 707

colloidal nanocrystal film that mitigates interfacial recombination and improves interface binding in low-temperature planar solar cells. We fabricated solar cells with certified efficiencies of 20.1 and 19.5% for active areas of 0.049 and 1.1 square centimeters, respectively, achieved via low-temperature solution processing. Solar cells with efficiency greater than 20% retained 90% (97% after dark recovery) of their initial performance after 500 hours of continuous room-temperature operation at their maximum power point under 1-sun illumination (where 1 sun is defined as the standard illumination at AM1.5, or 1 kilowatt/square meter).