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At least 1,225 records · Page 68

Partial Surface Selenization of Cobalt Sulfide Microspheres for Enhancing the Hydrogen Evolution Reaction

Electrocatalysis of water is a scalable and easily available source of the production of hydrogen (H 2 ), the future energy carrier. This drive for clean energy inspired us to develop an inexpensive, readily producible, highly active, and stable catalyst to replace current state of the art platinum catalysts. Building on the promising hydrogen evolution reaction (HER) activity of many pyrites, their structural tuning by different metals and nonmetals has been found to be effective in several instances. We present here one such effort by partial surface selenization of mesoporous cobalt sulfide material, which displayed long-term operational stability (for at least 25 h) besides attaining a current density of 100 mA cm –2 at an overpotential of 160 mV versus the reversible hydrogen electrode (RHE) (in acidic media). A low Tafel slope (of 52 mV dec –1 ) and high exchange current density ( j 0 ) (of 70 μA cm –2 ) make our catalyst better to most existing systems. More importantly, using a variety of analytical techniques, electrochemical measurements, and theoretical calculations, we have analyzed the morphology of the material and rationalized the key to the enhanced intrinsic activity (as compared to the meso-CoS 2 ) per active site. This study is expected to explain similar systems and modify approaches to enhancing the electrochemical activity of metal chalcogenides.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Methane Oxidation to Methanol Catalyzed by Cu-Oxo Clusters Stabilized in NU-1000 Metal–Organic Framework

The catalyzed conversion of shale gas-derived light hydrocarbons, e.g. methane to methanol, for further application as automotive fuels and/or bulk chemicals is especially attractive in light of improved methods of hydrocarbon extraction. MOF based catalysts have previously been demonstrated to be active for a range of catalytic reactions. In this work we used Cu-NU1000 as a methane-to-methanol oxidation catalyst. In addition to product studies, in-situ X-ray Absorption Spectroscopic (XAS) experiments are performed under catalytic conditions in order to follow the modification of the Cu-species and directly probe the structure/activity properties of the Cu-NU1000 system. The insights reported herein serve as a first look at metal-organic framework materials as catalysts for methane oxidation and be the basis for development of the subsequent generations of materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Strain stabilized nickel hydroxide nanoribbons for efficient water splitting

Development of efficient and durable oxygen evolution reaction (OER) catalysts has a direct impact on water splitting efficiency and cost effectiveness. In this work, we report the successful synthesis of a new Ni(OH) 2 structure, strain-stabilized Ni(OH) 2 nanoribbons (NR-Ni(OH) 2 ) two to three layers thick, with widths of 2-5 nm, via an electro-oxidation route. Conventional Ni(OH) 2 usually has negligible OER activity, while NR-Ni(OH) 2 shows a high activity for the oxygen evolution reaction, an overpotential of 162 millivolts and furthermore exhibits long-term stability in alkaline electrolyte. The substantial reduction in overpotential of NR-Ni(OH) 2 is due to its easier OOH* adsorption by the active four-coordinated Ni edge sites. The enhanced catalytic activity of NR-Ni(OH) 2 makes it an excellent candidate for industrial applications.

36 MATERIALS SCIENCE↗

An effective hybrid strategy for converting rice straw to furoic acid by tandem catalysisviaSn-sepiolite combined with recombinantE. coliwhole cells harboring horse liver alcohol dehydrogenase

The upgrading of biomass-derived furfural into high-value bio-based chemicals has attracted interest. In this case, the conversion of rice straw into furfural was firstly performed using tin-loaded sepiolite (Sn-sepiolite) as a catalyst. Acidified solid acid Sn-sepiolite (3.0 wt%) converted alkali-pretreated dewaxed rice straw into furfural at 42.2% yield at 170 °C for 20 min. Moreover, biomass-derived furfural could be completely converted into furoic acid with recombinant immobilized E. coli TS whole-cells within 96 h at pH 7.0 and 30 °C, respectively. Finally, efficient recycling and reuse of the Sn-sepiolite catalyst and immobilized TS whole-cell biocatalyst were developed for the synthesis of furoic acid from rice straw in the one-pot reaction system. In conclusion, an effective one-pot chemo-enzymatic synthesis of furoic acid from renewable biomass was successfully developed using ambient conditions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Elementary kinetics of nitrogen electroreduction on Fe surfaces

Electrochemical ammonia synthesis could provide a sustainable and efficient alternative to the energy intensive Haber-Bosch process. Development of an active and selective N 2 electroreduction catalyst requires mechanism determination to aid in connecting catalyst composition and structure to performance. Density functional theory calculations are used to examine the elementary step energetics of associative N 2 reduction mechanisms on two low index Fe surfaces. Interfacial water molecules in the Heyrovsky-like mechanism help lower some of the elementary activation barriers. Electrode potential dependent barriers show that cathodic potentials below -1.5 V-RHE are necessary to give a significant rate of N 2 electroreduction. DFT barriers suggest a larger overpotential than expected based on elementary reaction free energies. Linear Brønsted-Evans-Polanyi relationships do not hold across N–H formation steps on these surfaces, further confirming that explicit barriers should be considered in DFT studies of the nitrogen reduction reaction.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Planetary perspective. Report of Working Group Number 4

The study of global megageomorphology from a planetary perspective requires that, philosophically, we view the Earth as a planet like any other; one among a number of bodies of varied size and composition which, together with the Sun, form the Solar System. A first step in the study of the Earth from the planetary perspective is the development of global distribution maps of surface factors as landforms, tectonics, and of key processes operating on Earth. Data of other types, such as gravity and magnetism, should also be included and, so far as possible, multiple data sets should be developed. The compilation of maps would serve as a catalyst for research and a basis for interpretation. They could be used scientifically to document changes such as glacial variations and their relationships to climate, volcanic eruptions and their effects, and coastal alterations. Slow and rapid changes should be studied together with the relationships between scale and the rapidity of change. A study of the relationship of geomorphology (i.e., surficial processes) to lithology and structure is needed. The planetary perspective can also help in the identification and investigation of exotic features such as suspect terrains.

Rossbacher, L. A.↗

High Test Peroxide Incident at Stennis Space Center

A renewed interest n hydrogen peroxide as a rocket engine propellant has created a void in the experience base since the last era of significant peroxide use. Advanced catalyst beds and high concentration formulations are currently being developed and tested in the propulsion community. Although peroxide has many positive attributes, there are situations where peroxide must be handled with extreme care. An incident occurred at NASA's Stennis Space Center (SSC) in December 2000 where a significant over pressurization event damaged facility and test hardware. A description of the event and findings of the investigation board are presented and discussed.

Ross, R.↗

Performance of PEM Liquid-Feed Direct Methanol-Air Fuel Cells

A direct methanol-air fuel cell operating at near atmospheric pressure, low-flow rate air, and at temperatures close to 60oC would tremendously enlarge the scope of potential applications. While earlier studies have reported performance with oxygen, the present study focuses on characterizing the performance of a PEM liquid feed direct methanol-air cell consisting of components developed in house. These cells employ Pt-Ru catalyst in the anode, Pt at the cathode and Nafion 117 as the PEM. The effect of pressure, flow rate of air and temperature on cell performance has been studied. With air, the performance level is as high as 0.437 V at 300 mA/cm2 (90oC, 20 psig, and excess air flow) has been attained. Even more significant is the performance level at 60oC, 1 atm and low flow rates of air (3-5 times stoichiometric), which is 0.4 V at 150 mA/cm2. Individual electrode potentials for the methanol and air electrode have been separated and analyzed. Fuel crossover rates and the impact of fuel crossover on the performance of the air electrode have also been measured. The study identifies issues specific to the methanol-air fuel cell and provides a basis for improvement strategies.

Methanol-Air Fuel↗

Kinetic Measurements in Heterogeneous Catalysis

This contribution is about the experimental determination of the rate of a heterogeneous catalytic reaction and the analysis of kinetic data. In this case, the reaction rate can be defined as the frequency at which the closed sequence of elementary steps transforming reactants into products is occurring. However, the rate of chemical reaction is not directly observed; rather, one records the rate of substance change. The rate of chemical reaction is calculated based on the rate of substance change and assumed stoichiometry of the reaction. In order to make this an intensive quantity (i.e., independent of the volume in which the reaction is performed, this frequency is divided by the latter or by a quantity proportional to the latter). As the focus of what follows is on heterogeneously catalyzed reactions this can be the catalyst mass, the catalyst surface area or the total number of active sites present in the reaction volume confined by the walls of a chemical reactor. For example, the rate may be reported as one of the following: Net rate of consumption/production of component i mol m-3 s-1 Net specific rate of consumption/production of component i mol kg-1 s-1 Rate of substance change (per unit volume of catalyst) mol m-3 s-1 Specific reaction rate (per unit mass of catalyst) mol kg-1 s-1 Net rate of consumption/production of component i mol m-2 s-1 The turnover frequency (TOF) is a characteristic originally introduced by Boudart [1] is expressed as TOF=R/G_tot , where R is the steady-state rate of reactant consumption or product generation and G_totis the total areal density of active sites [mol m-2]. The latter is typically taken from experimental chemisorption data obtained at low temperature. The advancement of a chemical reaction leads to changes in the amounts of reactants and products which, for a stoichiometric single reaction, are connected by the stoichiometric coefficients. In many cases, for the sake of simplicity, we will assume that the investigated reaction proceeds according to a single reaction pathway, so that the net production rate of a reaction component is directly proportional to the reaction rate and that the latter equals the net production rate of any of the involved components when divided by the appropriate stoichiometric coefficient. For complex stoichiometric reactions the net production rates of the involved components are linear combinations of the reaction rates. Different goals for kinetic measurements can be formulated: Catalyst testing, i.e., obtaining the kinetic dependences for the development and discrimination of efficient catalytic materials. Precise kinetic characterization of active materials via high-throughput screening is a part of such activity. Detailed kinetics, i.e., revealing the detailed mechanism of complex catalytic reaction via systematic kinetic studies, both steady-state and non-steady-state Industrial kinetics, i.e., obtaining data and relationships for describing and predicting the behaviour of catalytic reactors and processes at industrial scale Finally, mathematical modeling and analysis where kinetic measurements provide data for understanding complex kinetic phenomena, e.g., oscillations, non-linear self-organization, etc.

36 MATERIALS SCIENCE↗

A Long-Cycle-Life Lithium-CO{sub 2} Battery with Carbon Neutrality.

Lithium-CO2 batteries are attractive energy-storage systems for fulfilling the demand of future large-scale applications such as electric vehicles due to their high specific energy density. However, a major challenge with Li-CO2 batteries is to attain reversible formation and decomposition of the Li2CO3 and carbon discharge products. A fully reversible Li-CO2 battery is developed with overall carbon neutrality using MoS2 nanoflakes as a cathode catalyst combined with an ionic liquid/dimethyl sulfoxide electrolyte. This combination of materials produces a multicomponent composite (Li2CO3/C) product. The battery shows a superior long cycle life of 500 for a fixed 500 mAh g(-1) capacity per cycle, far exceeding the best cycling stability reported in Li-CO2 batteries. The long cycle life demonstrates that chemical transformations, making and breaking covalent C-O bonds can be used in energy-storage systems. Theoretical calculations are used to deduce a mechanism for the reversible discharge/charge processes and explain how the carbon interface with Li2CO3 provides the electronic conduction needed for the oxidation of Li2CO3 and carbon to generate the CO2 on charge. This achievement paves the way for the use of CO2 in advanced energy-storage systems.

carbon neutrality↗

Physical-Chemical Solid Waste Processing for Space Missions at Ames Research Center

As space missions become longer in duration and reach out to more distant locations such as Mars, solids waste processing progresses from storage technologies to reclamation technologies. Current low Earth orbit technologies consist of store-and dispose to space or return to Earth. Fully regenerative technologies recycle wastes. The materials reclaimed from waste can be used to provide the basic materials to support plant growth for food including carbon dioxide, water, and nutrients. Other products can also be reclaimed from waste such as hydrocarbons and activated carbon. This poster describes development at Ames Research Center of a process to make activated carbon from space mission wastes and to make an incineration system that produces clean flue gas. Inedible biomass and feces contain hydrocarbons in a form that can be pyrolyzed and converted to activated carbon. The activated carbon can then be used to clean up contaminants from various other life support systems; in particular, the activated carbon can be used regeneratively to remove NOx from incinerator flue gas. Incinerator flue gas can also be cleaned up by the use of reductive and oxidative catalysts. A catalytic incinerator flue gas cleanup system has been developed at ARC that produces flue gas clean enough (with the exception of carbon dioxide) to meet the Space Minimum Allowable Concentration limits for human exposure.

Fisher, John W.↗

Interior Athabascan Energy Capacity Building Network (Final Report)

Tanana Chiefs Conference (TCC) is the traditional tribal consortium for the 37 federally recognized Tribes and villages of Interior Alaska. TCC is based on a belief in tribal self-determination and the need for regional Native unity. TCC is a nonprofit organization that works toward meeting the needs and challenges for more than 10,000 Alaska Natives (mostly Alaskan Athabaskans) in Interior Alaska. With support from DOE-OIE’s Inter-Tribal Technical Assistance grant, TCC’s goal was to expand and build on the solid foundation of work that the existing TCC Energy Program established through the creation of the Interior Athabascan Energy Network (IAEN). More specifically, the IAEN was designed to create a network of village-based energy champions across the interior and hold quarterly teleconferences and annual inperson meetings. Among the greatest impacts of the IAEN were the creation and support of realistic, communitybased energy projects that produced tangible results such as fuel savings and skills and capacity development among local staff as well as establishment of an energy team that included TCC staff, Tribal participants, technical consultants, and support agencies. The DOE-TA funding allowed us to provide technical assistance to our Tribal communities to develop energy projects, and to foster a network consisting of Tribal community members and energy experts that has strengthened the ability in the region to troubleshoot energy issues, develop meaningful projects, envision a clean energy future, and to share project successes and challenges. The funding from DOE was a catalyst for growth, has created opportunities for learning and knowledge sharing, and has led to the development of cost saving energy projects. Most importantly, the DOE project allowed energy champions around the region to share their knowledge, experiences, and expertise to create place-based solutions and has forged inter-Tribal relationships that will continue to be an asset for years to come. Through information exchange that occurred at out IAEN annual meetings and other events, this technical assistance grant award has spurred a spinoff project that is focused on establishing a collaborative of independent utilities that work together to solve energy problems and share services to operate and maintain their electric utilities. We have indentified at least 10 and possibly 12 communities that are interested in collaborating in managing their utilities to reduce costs and increase reliability. As well, by identifying and supporting Community Energy Champions in the Interior villages and adding capacity to the TCC Energy Program, we were able to create actionable community energy plans, develop specific projects, and increase local capacity, skills, and literacy around clean energy initiatives.

29 ENERGY PLANNING, POLICY, AND ECONOMY↗

Bridging the time scale in exascale computing of chemical systems (Final Technical Report)

This report summarizes the work carried out with support of the United States Department of Energy under Award DE-SC0019441. The theme of this project was to develop and apply methods that allowed for the acceleration of atomistic calculations, particularly in challenging areas such as multiphase systems, electrified interfaces, uncertainty estimation, and applications requiring chemical accuracy, which tend to be applications where simulation time is severely bottlenecked by the computational time requirements. Much of the focus was on the application of emerging machine-learning methodologies, although a wide range of methodologies were employed. This report has two major sections. The first focuses on the methodological advances themselves. Within this part, we report a number of major advances, a few examples of which are described here. We report the first machine-learning scheme for the acceleration of electronically grand-canonical calculations (that is, those applicable to electrochemistry). We report new methods of performing transfer learning, in which physics-based priors can be used to provide predictions, often with uncertainty estimates, of images well outside of training sets; we also offer ways to fine-tune these transfer-learning models. We provide a new systematic means to generate and apply minimal training data sets to very large (10,000’s of atoms) systems, with only small training sets appropriate for electronic structure. We developed new methodologies to integrate surface vibrations into surface adsorption calculations. We made advances to the applicability of diffusion Monte Carlo methods to allow (learned) force prediction, finite-size error correction, and force-free means of searching for transition states. We integrated machine-learned atomistic predictions into mechanism generation codes. Additionally, we released new software including AmpTorch, a modernized version of our original atomistic machine-learning code Amp. The second part of this report focuses on the scientific applications that accompanied, and were often enabled by, the methodological advances described earlier. A few examples follow, but full details are in the individual chapters of the report. For example, we developed a general theory of phonon-induced friction on molecular adsorbates. We showed fundamentally how solvent influences the adsorption and desorption process and how it differs from the processes typically involved at the solid–gas interface, making aqueous-phase and electrocatalysis different from traditional thermocatalysis. We examined how metal–insulator and magnetic transitions can be probed, and accelerated exciton dynamics via Frenkel Hamiltonian parameters. We showed that the nearsighted force-training approach, developed within this project, can predict both the stability and reactivity of large nanoparticles, and can also lead to insights on catalyst coverage on binding energies and entropies. These applied studies, which generally integrated with our method development, allowed us to push forward the theoretical understanding of several reaction classes.

08 HYDROGEN↗

Indirect Liquefaction of Coal-Biomass Mixture for Production of Jet Fuel with High Productivity and Selectivity

Coal to liquids (CTL) and coal-biomass to liquids (CBTL) processes were advanced by testing and demonstrating Southern Research’s sulfur tolerant nickel-based reforming catalyst and Chevron’s highly selective and active cobalt-zeolite hybrid Fischer-Tropsch (FT) catalyst to clean, upgrade and convert syngas predominantly to jet fuel range hydrocarbon liquids, thereby minimizing expensive cleanup and wax upgrading operations. The National Carbon Capture Center (NCCC) operated by Southern Company (SC) at Wilsonville, Alabama served as the host site for the gasifier slip-stream and simulated syngas testing/demonstration. Reformer testing was performed to (1) reform tar and light hydrocarbons, (2) decompose ammonia in the presence H2S, and (3) deliver the required H2 to CO ratio for FT synthesis. FT Testing was performed to produce a product primarily containing C5-C20 liquid hydrocarbons and no C21+ waxy hydrocarbons with productivity greater than 0.7 gC5+/g catalyst/h, and at least 70% diesel and jet fuel range (C8-C20) hydrocarbon selectivity in the liquid product. A novel heat-exchange reactor system was employed to enable the use of the highly active FT catalyst and larger diameter reactors that results in cost reduction for commercial systems. Following laboratory development and testing, SR’s laboratory reformer was modified to operate in a Class 1 Div. 2 environment, installed at NCCC, and successfully tested for 125 hours using raw syngas. The catalyst demonstrated near equilibrium reforming (~90%) of methane and complete reforming/decomposition of tar and ammonia in the presence of up to 380 ppm H2S. For FT synthesis, SR modified and utilized a bench scale skid mounted FT reactor system (SR-CBTL test rig) that was fully integrated with a slip stream from SC/NCCC’s transport gasifier (TRIG). The test-rig developed in a previous project (DE-FE0010231) was modified to receive up to 7.5 lb/h raw syngas augmented with bottled syngas to adjust the H2/CO molar ratio to 2, clean it to cobalt FT catalyst specifications, and produce liquid FT products at the design capacity of up to 6 L/day. Promising Chevron catalyst candidates in the size range from 70-200 μm were loaded onto SR’s 2-inch ID and 4-inch ID bench-scale reactors utilizing IntraMicron’s micro-fiber entrapped catalyst (MFEC) heat exchange reactor technology. During 2 test campaigns, the FT reactors were successfully demonstrated at NCCC using syngas for ~420 hours. The catalyst did not experience deactivation during the tests. SR’s thermo-syphon heat removal system maintained reactor operating temperature along the axis to within ±4 °C. The experiments gave a steady catalyst productivity of 0.7-0.8 g/g catalyst/h, liquid hydrocarbon selectivity of ~75%, and diesel and jet fuel range hydrocarbon selectivity in the liquid product as high as 85% depending on process conditions. A preliminary techno-economic evaluation showed that the SR technology-based 50,000 bpd plant had a 10 % lower total plant cost compared to a conventional slurry reactor based plant. Furthermore, because of the modular nature of the SR technology, it was shown that the total plant cost advantage increases to >35 % as the plant is scaled down to 1000 bpd.

01 COAL, LIGNITE, AND PEAT↗

Antioxidant-induced transformations of a metal-acid hydrocracking catalyst in the deconstruction of polyethylene waste

Plastics are ideal for numerous applications, as driven by the development of complex formulations containing various additives to improve performance and processability. Unfortunately, chemical valorization strategies (e.g., catalytic deconstruction) often can be challenged by the presence of small-molecule additives, and quantification of the impact of these molecular constituents on upcycling processes remains elusive. Here, this dearth of information restricts catalyst design efforts to combine the robustness and performance necessary to improve plastics circularity. In this communication, we describe a systematic study of common plastics additives—phenolic antioxidants, and we quantify the relationship between additive content and deconstruction yields of high-density polyethylene (HDPE) over a platinum on tungstated zirconium (Pt/WO 3 /ZrO 2 ) hydrocracking catalyst. In the simplest case of a base (antioxidant- and slip agent-containing) HDPE resin versus a pure (additive-stripped) HDPE polymer, a two-fold decrease in the yield of gas and liquid products is noted for base HDPE resin. Furthermore, both antioxidant chemistry and concentration strongly impact conversion and individual product selectivities. Using infrared spectroscopy, we determine that antioxidants change the effective ratio of metal to acid sites (i.e., metal-acid balance) through reactions of phenols and/or other functional groups (e.g., acids, esters) with catalyst active sites. Overall, this work demonstrates the impact of one common set of additives on plastics deconstruction, and the analysis herein provides a blueprint for quantitatively assessing the effects of additives on plastics deconstruction processes and for evaluating the development of more robust catalytic strategies or more tolerable additive formulations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

P‐Doping Modulated RuIr Nanoparticles Anchored on Co/N/C Catalysts with Improved Alkaline Hydrogen Evolution Activity and Stability

Achieving efficient and stable hydrogen evolution reactions in alkaline conditions is crucial for hydrogen production. In this study, a RuIr/Co (SA) NC-P catalyst featuring RuIr alloys alongside P-doping and CoNx sites is developed. RuIr alloying optimizes the electronic structure between Ru and Ir, promoting electron transfer from Ru to Ir. P-doping further modulates the electronic properties of RuIr alloys, optimizing hydrogen binding energy and weakening Ru─OH binding energy, facilitating rapid H 2 generation and OH ad transfer. Meanwhile, CoNx promotes water dissociation, providing a fast proton delivery path for RuIr alloys. The catalyst exhibits enhanced HER activity with a low overpotential of 20 mV at 10 mA cm −2 , a Tafel slope of 20.4 mV dec −1 , and a turnover frequency of 19.5 H 2 s −1 at 150 mV overpotential. Moreover, catalyst stability is improved 8 times by mitigating RuIr alloy dissolution/agglomeration via P-doping. In conclusion, this work introduces a promising approach for developing efficient and stable HER electrocatalysts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

An Intensified Electro-Catalytic Process for Production of Formic Acid from Power Plant CO 2 Emissions (Final Technical Report)

The goal of this project was to develop and test a novel electro-catalytic method for the production of high-value formic acid from coal-derived CO 2 as a strategy to offset the cost of CO 2 capture. Formic acid is currently produced from the conversion of higher-order carbon products such as methane and/or methanol. This electro-catalytic CO 2 reduction process utilizes a highly selective catalyst in a flow-through reactor design to maximize the formic acid production rate. The specific objectives of this proposed study were to; 1) produce and screen highly selective engineered CO 2 reducing catalysts capable of exclusively producing formic acid; 2) immobilize the catalyst within a flow process to continually produce formic acid and increase catalyst lifetime; and 3) assess the stability of the electrocatalyst during long-term operation. The project involved the development and testing of an engineered catalyst to selectively reduce CO 2 directly and exclusively to formic acid. After the best-performing catalyst was selected, it was immobilized and tested inside a flow-through reactor at UK CAER using realistic conditions expected from CO 2 produced during coal combustion and separated by a CO 2 capture plant.

01 COAL, LIGNITE, AND PEAT↗

Single‐Atom Electrocatalysts from Multivariate Metal–Organic Frameworks for Highly Selective Reduction of CO 2 at Low Pressures

Abstract Single‐atom catalysts (SACs) are of great interest because of their ultrahigh activity and selectivity. However, it is difficult to construct model SACs according to a general synthetic method, and therefore, discerning differences in activity of diverse single‐atom catalysts is not straightforward. Herein, a general strategy for synthesis of single‐atom metals implanted in N‐doped carbon (M 1 ‐N‐C; M=Fe, Co, Ni and Cu) has been developed starting from multivariate metal–organic frameworks (MOFs). The M 1 ‐N‐C catalysts, featuring identical chemical environments and supports, provided an ideal platform for differentiating the activity of single‐atom metal species. When employed in electrocatalytic CO 2 reduction, Ni 1 ‐N‐C exhibited a very high CO Faradaic efficiency (FE) up to 96.8 % that far surpassed Fe 1 ‐, Co 1 ‐ and Cu 1 ‐N‐C. Remarkably, the best‐performer, Ni 1 ‐N‐C, even demonstrated excellent CO FE at low CO 2 pressures, thereby representing a promising opportunity for the direct use of dilute CO 2 feedstock.

Jiao, Long↗