BACKGROUND With a rising global population, increasing energy demands, and impending climate change, major concerns have been raised over the security of our energy future. Developing sustainable, fossil-free pathways to produce fuels and chemicals of global importance could play a major role in reducing carbon dioxide emissions while providing the feedstocks needed to make the products we use on a daily basis. One prospective goal is to develop electrochemical conversion processes that can convert molecules in the atmosphere (e.g., water, carbon dioxide, and nitrogen) into higher-value products (e.g., hydrogen, hydrocarbons, oxygenates, and ammonia) by coupling to renewable energy. Electrocatalysts play a key role in these energy conversion technologies because they increase the rate, efficiency, and selectivity of the chemical transformations involved. Today’s electrocatalysts, however, are inadequate. The grand challenge is to develop advanced electrocatalysts with the enhanced performance needed to enable widespread penetration of clean energy technologies. ADVANCES Over the past decade, substantial progress has been made in understanding several key electrochemical transformations, particularly those that involve water, hydrogen, and oxygen. The combination of theoretical and experimental studies working in concert has proven to be a successful strategy in this respect, yielding a framework to understand catalytic trends that can ultimately provide rational guidance toward the development of improved catalysts. Catalyst design strategies that aim to increase the number of active sites and/or increase the intrinsic activity of each active site have been successfully developed. The field of hydrogen evolution, for example, has seen important breakthroughs over the years in the development of highly active non–precious metal catalysts in acid. Notable advancements have also been made in the design of oxygen reduction and evolution catalysts, although there remains substantial room for improvement. The combination of theory and experiment elucidates the remaining challenges in developing further improved catalysts, often involving scaling relations among reactive intermediates. This understanding serves as an initial platform to design strategies to circumvent technical obstacles, opening up opportunities and approaches to develop higher-performance electrocatalysts for a wide range of reactions. OUTLOOK A systematic framework of combining theory and experiment in electrocatalysis helps to uncover broader governing principles that can be used to understand a wide variety of electrochemical transformations. These principles can be applied to other emerging and promising clean energy reactions, including hydrogen peroxide production, carbon dioxide reduction, and nitrogen reduction, among others. Although current paradigms for catalyst development have been helpful to date, a number of challenges need to be successfully addressed in order to achieve major breakthroughs. One important frontier, for example, is the development of both experimental and computational methods that can rapidly elucidate reaction mechanisms on broad classes of materials and in a wide range of operating conditions (e.g., pH, solvent, electrolyte). Such efforts would build on current frameworks for understanding catalysis to provide the deeper insights needed to fine-tune catalyst properties in an optimal manner. The long-term goal is to continue improving the activity and selectivity of these catalysts in order to realize the prospects of using renewable energy to provide the fuels and chemicals that we need for a sustainable energy future.

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Combining theory and experiment in electrocatalysis: Insights into materials design

This paper reviews recent progress made in identifying electrocatalysts for carbon dioxide (CO2) reduction to produce low-carbon fuels, including CO, HCOOH/HCOO−, CH2O, CH4, H2C2O4/HC2O4−, C2H4, CH3OH, CH3CH2OH and others. The electrocatalysts are classified into several categories, including metals, metal alloys, metal oxides, metal complexes, polymers/clusters, enzymes and organic molecules. The catalyts' activity, product selectivity, Faradaic efficiency, catalytic stability and reduction mechanisms during CO2 electroreduction have received detailed treatment. In particular, we review the effects of electrode potential, solution–electrolyte type and composition, temperature, pressure, and other conditions on these catalyst properties. The challenges in achieving highly active and stable CO2 reduction electrocatalysts are analyzed, and several research directions for practical applications are proposed, with the aim of mitigating performance degradation, overcoming additional challenges, and facilitating research and development in this area.

A review of catalysts for the electroreduction of carbon dioxide to produce low-carbon fuels

To date, copper is the only heterogeneous catalyst that has shown a propensity to produce valuable hydrocarbons and alcohols, such as ethylene and ethanol, from electrochemical CO2 reduction (CO2R). There are variety of factors that impact CO2R activity and selectivity, including the catalyst surface structure, morphology, composition, the choice of electrolyte ions and pH, and the electrochemical cell design. Many of these factors are often intertwined, which can complicate catalyst discovery and design efforts. Here we take a broad and historical view of these different aspects and their complex interplay in CO2R catalysis on Cu, with the purpose of providing new insights, critical evaluations, and guidance to the field with regard to research directions and best practices. First, we describe the various experimental probes and complementary theoretical methods that have been used to discern the mechanisms by which products are formed, and next we present our current understanding of the complex reaction networks for CO2R on Cu. We then analyze two key methods that have been used in attempts to alter the activity and selectivity of Cu: nanostructuring and the formation of bimetallic electrodes. Finally, we offer some perspectives on the future outlook for electrochemical CO2R.

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Progress and Perspectives of Electrochemical CO2 Reduction on Copper in Aqueous Electrolyte

Conversion of carbon dioxide (CO2) to carbon monoxide (CO) and other value-added carbon products is an important challenge for clean energy research. Here we report modular optimization of covalent organic frameworks (COFs), in which the building units are cobalt porphyrin catalysts linked by organic struts through imine bonds, to prepare a catalytic material for aqueous electrochemical reduction of CO2 to CO. The catalysts exhibit high Faradaic efficiency (90%) and turnover numbers (up to 290,000, with initial turnover frequency of 9400 hour(-1)) at pH 7 with an overpotential of -0.55 volts, equivalent to a 26-fold improvement in activity compared with the molecular cobalt complex, with no degradation over 24 hours. X-ray absorption data reveal the influence of the COF environment on the electronic structure of the catalytic cobalt centers.

/pdf/covalent-organic-frameworks-comprising-cobalt-porphyrins-for-16e0bybrm3.pdf

Covalent organic frameworks comprising cobalt porphyrins for catalytic CO2 reduction in water

The applications of copper (Cu) and Cu-based nanoparticles, which are based on the earth-abundant and inexpensive copper metal, have generated a great deal of interest in recent years, especially in the field of catalysis. The possible modification of the chemical and physical properties of these nanoparticles using different synthetic strategies and conditions and/or via postsynthetic chemical treatments has been largely responsible for the rapid growth of interest in these nanomaterials and their applications in catalysis. In addition, the design and development of novel support and/or multimetallic systems (e.g., alloys, etc.) has also made significant contributions to the field. In this comprehensive review, we report different synthetic approaches to Cu and Cu-based nanoparticles (metallic copper, copper oxides, and hybrid copper nanostructures) and copper nanoparticles immobilized into or supported on various support materials (SiO2, magnetic support materials, etc.), along with their applications i...

http://pubs.acs.org/doi/pdfplus/10.1021/acs.chemrev.5b00482

Cu and Cu-Based Nanoparticles: Synthesis and Applications in Catalysis.

Single-atom functionalization of transition-metal dichalcogenide (TMD) nanosheets is a powerful strategy to tune the optical, magnetic, and catalytic properties of two-dimensional materials. In thi...

Solution-Phase Activation and Functionalization of Colloidal WS2 Nanosheets with Ni Single Atoms.

Core–shell nanoparticles of Au@Pd with precise submonolayer, monolayer, or multilayer structure were synthesized using ligand-exchange reactions of palladate ions onto colloidal Au nanocrystals. Decoupling the palladate adsorption step from the subsequent reduction enables excellent precision, uniformity, and tunability in the Pd shell thickness. The redox properties of the surface Pd are directly correlated to the thickness of the Pd shell with a >+200 mV shift in the PdO reduction potential for submonolayer Au@Pd nanoparticles compared to pure Pd. Using these precisely controlled core–shell materials, the oxygen reduction catalytic activity can be directly correlated to PdO reduction potential and Pd surface coverage on Au. When the Pd oxide reduction peak is shifted by +240 mV compared to pure Pd, a 50 mV reduction in overpotential and a 4-fold increase in kinetic current density for oxygen reduction are observed. Colloidal ligand-exchange synthesis may be particularly useful for noble metal core–shell...

Systematic Control of Redox Properties and Oxygen Reduction Reactivity through Colloidal Ligand-Exchange Deposition of Pd on Au.

Precise synthesis and characterization of bimetallic nanoparticles are critical toward understanding structure–activity relationships in alkane dehydrogenation catalysis. Traditional synthetic meth...

Colloidal Synthesis of Well-Defined Bimetallic Nanoparticles for Nonoxidative Alkane Dehydrogenation

A method for electrochemically reducing CO 2 is provided. A cathode is provided, wherein the cathode comprises a conductive substrate with a catalyst of a metal and a metal oxide based coating on a side of the cathode. An anode is spaced apart from the cathode. An ionic transport is provided between the anode and cathode. The cathode is exposed to CO 2 and H 2 O. The anode is exposed to H 2 O. A voltage is provided between the cathode and anode.

Catalysts for low temperature electrolytic co2 reduction

Understanding the microstructural evolution of bimetallic Pt nanoparticles under electrochemical polarization is critical to developing durable fuel cell catalysts. In this work, we develop a colloidal synthetic method to generate core-shell Au@Pt nanoparticles of varying surface Pt coverages to understand how as-synthesized bimetallic microstructure influences nanoparticle structural evolution during formic acid oxidation. By comparing the electrochemical and structural properties of our Au@Pt core-shells with bimetallic AuPt alloys at various stages in catalytic cycling, we determine that these two structures evolve in divergent ways. In core-shell nanoparticles, Au atoms from the core migrate outward onto the surface, generating transient "single-atom" Pt active sites with high formic acid oxidation activity. Metal migration continues until Pt is completely encapsulated by Au, and catalytic reactivity ceases. In contrast, AuPt alloys undergo surface dealloying and significant leaching of Pt out of the nanoparticle. Elucidating the dynamic restructuring processes responsible for high electrocatalytic reactivity in Pt bimetallic structures will enable better design and predictive synthesis of nanoparticle catalysts that are both active and stable.

Christina W. Li

Papers

Solution-Phase Activation and Functionalization of Colloidal WS2 Nanosheets with Ni Single Atoms.

Systematic Control of Redox Properties and Oxygen Reduction Reactivity through Colloidal Ligand-Exchange Deposition of Pd on Au.

Colloidal Synthesis of Well-Defined Bimetallic Nanoparticles for Nonoxidative Alkane Dehydrogenation

Catalysts for low temperature electrolytic co2 reduction

Microstructural Evolution of Au@Pt Core-Shell Nanoparticles under Electrochemical Polarization.