Carbon Dioxide Electroreduction Research Articles

Unravelling the Effect of Crystal Facet of Derived-Copper Catalysts on the Electroreduction of Carbon Dioxide under Unified Mass Transport Condition.

Altering the physical structure and chemical property of copper, i.e., particle size, surface morphology, composition or crystal facet, has been demonstrated to be effective in steering the selectivity of products in electrochemical reduction of carbon dioxide. However, these modifications generally result in the change of active surface area, leading to differences in the geometric current density and local pH, which are also demonstrated to be the key factors for observed selectivity change. In this work, we deconvolute the effect of mass transport and local pH from the effect of crystal facet by investigating five copper-based catalysts with identical roughness factors for electrochemical reduction of carbon dioxide in an H-cell. Interestingly, CuO-derived catalyst stands out as the best catalyst for C-C coupling. At -1.07 V vs. RHE, the faradaic efficiency of C2+ product reaches 44.3%, with a partial current density of -10.8 mA cm-2. Electrochemical adsorption of *OH reveals that the C2+ product selectivity of derived-copper catalysts correlates positively with the ratio of Cu(100)/Cu(110) of five catalysts. Additionally, in situ Raman spectroscopy reveals that the percentage of low-frequency band linear CO (LFB-CO), which is attributed to the adsorbed *CO on Cu(100) facet, increases with the C-C coupling efficiency.

Unravelling the Effect of Crystal Facet of Derived‐Copper Catalysts on the Electroreduction of Carbon Dioxide under Unified Mass Transport Condition

Altering the physical structure and chemical property of copper, i.e., particle size, surface morphology, composition or crystal facet, has been demonstrated to be effective in steering the selectivity of products in electrochemical reduction of carbon dioxide. However, these modifications generally result in the change of active surface area, leading to differences in the geometric current density and local pH, which are also demonstrated to be the key factors for observed selectivity change. In this work, we deconvolute the effect of mass transport and local pH from the effect of crystal facet by investigating five copper‐based catalysts with identical roughness factors for electrochemical reduction of carbon dioxide in an H‐cell. Interestingly, CuO‐derived catalyst stands out as the best catalyst for C‐C coupling. At ‐1.07 V vs. RHE, the faradaic efficiency of C2+ product reaches 44.3%, with a partial current density of ‐10.8 mA cm‐2. Electrochemical adsorption of *OH reveals that the C2+ product selectivity of derived‐copper catalysts correlates positively with the ratio of Cu(100)/Cu(110) of five catalysts. Additionally, in situ Raman spectroscopy reveals that the percentage of low‐frequency band linear CO (LFB‐CO), which is attributed to the adsorbed *CO on Cu(100) facet, increases with the C‐C coupling efficiency.

Back Cover: Metal–Organic Framework Supported Low‐Nuclearity Cluster Catalysts for Highly Selective Carbon Dioxide Electroreduction to Ethanol

Back Cover: Metal–Organic Framework Supported Low‐Nuclearity Cluster Catalysts for Highly Selective Carbon Dioxide Electroreduction to Ethanol

Back Cover: Metal–Organic Framework Supported Low‐Nuclearity Cluster Catalysts for Highly Selective Carbon Dioxide Electroreduction to Ethanol

Back Cover: Metal–Organic Framework Supported Low‐Nuclearity Cluster Catalysts for Highly Selective Carbon Dioxide Electroreduction to Ethanol

Bismuth oxide nanoflakes grown on defective microporous carbon endows high-efficient CO2 reduction at ampere level

Carbon dioxide electroreduction is a green technology for artificial carbon sequestration, which is being delayed from industrialization due to the lack of efficient catalysts at high current conditions. Herein, the Bi2O3 nanoflakes were uniformly grown on a defective porous carbon (PC). This self-assembling Bi2O3/PC catalyst was applied to drive CO2 electroreduction at 1.0 A, 1.5 A and 2.0 A while the Faradaic efficiency of formate reaches 91.50 %, 86.30 % and 84.22 %, respectively. Density functional theory calculations revealed the intrinsic defect of carbon is able to give electron to Bi through O bridge, which increased the electron aggregation of Bi and lowered the generation energy barrier of *OCHO intermediate. Additionally, the unique 3D network of staggered Bi2O3 enhances the CO2 adsorption and favors the electron transportation. By integrating all above advantages into a solid electrolyte-type cell, we are able to produce pure formic acid in a rate of 15.48 mmol h−1 at ampere current.

Pressure-induced generation of heterogeneous electrocatalytic metal hydride surfaces for sustainable hydrogen transfer

Metal hydrides are crucial intermediates in numerous catalytic reactions. Intensive efforts have been dedicated to constructing molecular metal hydrides, where toxic precursors and delicate mediators are usually involved. Herein, we demonstrate a facile pressure-induced methodology to generate a cost-effective heterogeneous electrocatalytic metal hydride surface for sustainable hydrogen transfer. Taking carbon dioxide (CO2) electroreduction as a model system and zinc (Zn), a well-known carbon monoxide (CO)-selective catalyst, as a model catalyst, we showcase a homogeneous-type hydrogen atom transfer process induced by heterogeneous hydride surfaces, enabling direct hydrogenation pathways traditionally considered “prohibited”. Specifically, the maximal Faradaic efficiency for formate is enhanced by ~fivefold to 83% under ambient conditions. Experimental and theoretical analyses reveal that unlike the distal hydrogenation route for CO2 to CO over pristine Zn, the Zn hydride surface enables direct hydrogenation at the carbon site of CO2 to form formate. This work provides a promising material platform for sustainable synthesis.

In2O3/Bi2O3 interface induces ultra-stable carbon dioxide electroreduction on heterogeneous InBiOx catalyst

The electrochemical reduction of CO2 (ERCO2) has emerged as one of the most promising methods for achieving both renewable energy storage and CO2 recovery. However, achieving both high selectivity and stability of catalysts remains a significant challenge. To address this challenge, this study investigated the selective synthesis of formate via ERCO2 at the interface of In2O3 and Bi2O3 in the InBiO6 composite material. Moreover, InBiO6 was synthesized using indium-based metal–organic frameworks as precursor, which underwent continuous processing through ion exchange and thermal reduction. The results revealed that the formate Faradaic efficiency (FEformate) of InBiO6 reached nearly 100 % at −0.86 V vs. reversible hydrogen electrode (RHE) and remained above 90 % after continuous 317-h electrolysis, which exceeded those of previously reported indium-based catalysts. Additionally, the InBiO6 composite material exhibited an FEformate exceeding 80 % across a wide potential range of 500 mV from −0.76 to −1.26 V vs. RHE. Density-functional theory analysis confirmed that the heterogeneous interface of InBiO6 played a role in achieving optimal free energies for *OCHO on its surface. Furthermore, the addition of Bi to the InBiO6 matrix facilitated electron transfer and altered the electronic structure of In2O3, thereby enhancing the adsorption, decomposition, and formate production of *OCHO.

Copper-Based Metal–Organic Frameworks Applied as Electrocatalysts for the Electroreduction of Carbon Dioxide (CO2ER) to Methane: A Review

The electrochemical reduction of carbon dioxide (CO2) to methane (CH4) holds tremendous potential in mitigating greenhouse gas emissions and producing renewable fuels. Thus, this review provides a comprehensive overview of the utilization of copper-based metal–organic frameworks (Cu-MOFs) as catalysts for this transformative process. Diverse key aspects of Cu-MOFs that make them ideal candidates for CO2 reduction are discussed, including their high surface areas, tunable pore sizes, and customizable active sites. Furthermore, recent advances in the design and synthesis of Cu-MOFs tailored specifically for enhanced catalytic activity and selectivity towards CH4 production are highlighted. Additionally, mechanistic insights into the CO2 reduction process on Cu-MOF catalysts are examined. Moreover, the recent application of diverse Cu-MOFs and derived materials in electrochemical reduction systems is discussed, and future research directions and potential applications of Cu-MOFs in sustainable energy conversion technologies are outlined. Thus, this review provides valuable insights into the current state of the art and the prospects for utilizing Cu-MOFs as efficient catalysts for the electrochemical conversion of CO2 to CH4, offering a pathway towards a greener and more sustainable energy future.

Electrochemical and Photoelectrochemical Reduction of Carbon Dioxide on Ruthenium-Cultured Bacterial Biofilms

Most of the bacterial species form biofilms, in which microorganisms are attached to a surface and they are held together by extracellular polymeric substances that they produce. They tend to grow almost everywhere both on living or non-living surfaces. Biofilms are able to propagate charge within their structures and to transfer effectively electrons at interfaces, as well as they could exhibit electrocatalytic properties (e.g. in Microbial Fuels Cells). The application of microbes provides better flexibility: experiments with fuel cells can be operated at normal conditions (temperatures and pressures). Wide variety of microbial metabolic pathways gives the possibility to use aggregates of bacteria in diverse processes. Proposed electrochemical studies using bacterial biofilms (in the form of thin coatings on the glassy carbon electrodes) can be considered as an attempt to find efficient methods of using the energy produced by microorganisms and converting it to electricity.The ultimate goal of the present research has been to determine whether it is possible under laboratory conditions to perform electrocatalytic processes using the hybrid (composite) layers composed of aggregates of bacteria in pristine or modified forms. A biofilm formed by a strain of Yersinia enterocolitica (Y. enterocolitica) is characterized by a high physicochemical stability over a wide pH range (4-10) and temperatures (0-40°C).The subject of interest is a fairly complex reaction, electroreduction of carbon dioxide. There has been growing interest in the search of electrocatalytic anf photoelectrochemical systems capable of efficient conversion of carbon dioxide into fuels and utility chemicals. Our previously performed studies have clearly shown that the Y. enterocolitica biofilm itself has no activity with respect to reduction of CO2, however it acts as a good matrix for the catalytic (e.g. noble metal or metaloorganic) centers, because it affects the reaction mechanism and appears to decrease overpotential of the electroreduction processes. The conducted research shows that the composite materials containing bacterial biofilms can be successfully used to construct systems that have an electrocatalytic reactivity in the reduction of carbon dioxide. We will also address the possibility of dispersing the organometallic ruthenium (II) complex in the biological layer (biofilm). Indeed, the ruthenium (II) complex has been immobilized in the biofilm matrix by successive modification of the liquid medium (Luria-Bertani medium) for culturing bacteria with a solution of the complex compound. In addition, the biological matrix was used (along with the ruthenium (II) complex molecules dispersed in its layer) as a protective coating, stabilizing the unstable p-type semiconductor - copper (I) oxide. The proposed hybrid co-catalytic system showed activity during the photoelectrochemical reduction of carbon dioxide and stability under semi-neutral experimental conditions. Finally, we are going to address the design of the above-mentioned catalytically active systems emphasizing the need to control the structure of the studied hybrid materials (in addition to their stability). Among important issues is the viability of bacteria in the biological membrane as well as elucidation of the role of the bacterial biofilm during the carbon dioxide reduction.

(Invited) First Principles Treatments of Heterogeneous Electrocatalysis – Reactivity Trends and Electrocatalyst Structure

Advances in the theoretical understanding of electrochemical systems have, over the past decade, led to growing use of periodic Density Functional Theory studies to treat a surprisingly large ensemble of electrocatalytic reactions, ranging from carbon dioxide electroreduction to oxygen evolution. Many such studies have employed simplified models of the electrochemical environment to determine reactivity trends across a broad space of catalytic materials, while other efforts have focused on developing detailed descriptions of electrochemical phenomena, such as the structure of electrochemical double layers, on model catalyst structures. An emerging challenge is to combine these approaches to ultimately enable theoretical design of electrocatalysts for reactions of significantly expanded chemical and materials complexity.In this talk, I will begin by discussing how we have applied strategies from computational heterogeneous catalysis to design enhanced electrocatalysts for the classic oxygen reduction reaction. In such treatments, we have effected highly detailed analyses of the catalyst surface structure and have employed machine learning-based methods to describe interactions between the various ORR reaction intermediates that are present at significant surface coverages. I will then explore challenges in obtaining more detailed descriptions of the electrocatalytic reaction environment, including the structure of catalysts with solid/solid interfaces, the distribution of charges in electrochemical double layers, and the structure and entropy of solvents near the electrocatalyst surface. I will conclude with some perspectives on how these complexities may be incorporated into traditional computational catalyst screening approaches to identify improved materials for more complex electrocatalytic systems.

Photothermal Assisted Biomass Oxidation for Pairing Carbon Dioxide Electroreduction with Low Cell Potential.

Integrating anodic biomass valorization with carbon dioxide electroreduction (CO2RR) can produce value-added chemicals on both the cathode and anode; however, anodic oxidation still suffers from high overpotential. Herein, a photothermal-assisted method was developed to reduce the potential of 5-hydroxymethyl furfural (HMF) electrooxidation. Capitalizing on the copious oxygen vacancies, defective Co3O4 (D-Co3O4) exhibited a stronger photothermal effect, delivering a local temperature of 175.47 °C under near infrared light illumination. The photothermal assistance decreased the oxidation potential of HMF from 1.7 V over pristine Co3O4 to 1.37 V over D-Co3O4 to achieve a target current density of 30 mA cm-2, with 2,5-furandicarboxylic acid as the primary product. Mechanistic analysis disclosed that the photothermal effect did not change the HMF oxidation route but greatly enhanced the adsorption capacity of HMF. Meanwhile, faster electron transfer for direct HMF oxidation and the surface conversion to cobalt (oxy)hydroxide, which contributed to indirect HMF oxidation, was observed. Thus, rapid HMF conversion was realized, as evidenced by in situ surface-enhanced infrared spectroscopy. Upon coupling cathodic CO2RR with an atomically dispersed Ni-N/C catalyst, the Faradaic efficiencies of CO (cathode) and 2,5-furandicarboxylic acid (FDCA, anode) exceeded 90.0 % under a low cell potential of 1.77 V.

Operando Investigation of the Origin of C─C Coupling in Electrochemical CO2 Reduction Upon Releasing Bonding Strength, Structural Ordering in Pd─Cu Catalyst

AbstractIt is widely established that the electroreduction of carbon dioxide on a copper surface yields a spectrum of alcohols and hydrocarbons. But the selectivity of Cu toward a certain product is extremely poor as it forms a variety of reduced products concurrently. Controlling selectivity and overall performance depends on the modification of the Cu site and local environment. This study depicts how the product selectivity can be switched from C1 to C2 and multicarbon products by systematic incorporation of secondary metal (Pd) into the Cu lattice. Upon releasing the structural ordering from intermetallic to alloy and then to bimetallic, a systematic enhancement on the formation of C2 products from CO2 has been observed. Real‐time in situ X‐ray absorption spectroscopy (XAS) study showed the potential dependent evolution of Pd─Cu and Cu─Cu bonds in different Pd‐Cu‐based catalysts. The detailed analysis of in situ IR and Raman also determined the adsorbed intermediate species and helped to identify the mechanism. Computational studies show the feasibility of multicarbon product formation on bimetallic catalysts compared to alloy and intermetallic catalysts. The current density and the activity of the CO2 electroreduction have been enhanced by the utilization of the flow cell in the gas diffusion electrode configuration.

Fabrication of indium doped Bi/Bi2O3 catalyst for efficiently selective electroreduction of carbon dioxide to formate

Highly selective electrocatalytic reduction of CO2 to formate is considered a valid route for alleviating the continuing increase in atmospheric CO2 concentration. Herein, Indium-doped Bi/Bi2O3 (In-Bi/Bi2O3) electrocatalyst grown in situ on carbon paper (CP) was obtained via a relatively simple one-step solvothermal synthesis method and utilized in CO2 reduction reaction (CO2RR) for formate production. The In-Bi/Bi2O3/CP exhibits superior Faradaic Efficiency for formate, i.e., FEformate = 96.3 %, and a partial current density of 6.74 mA cm−2 at −1.6 V (vs Ag/AgCl) in the H-type cell. Furthermore, FEformate of the electrode remains consistently above 90 % within long-term stability testing (60 h). By density functional theory (DFT) calculations, it is found that incorporating In into Bi/Bi2O3 can generate more active sites and facilitate the preferential adsorption of *OOCH intermediates, alleviating competitive adsorption of *H during CO2 reduction reaction (CO2RR), thereby accelerating formate production.

Dramatic Improvement of Homogeneous Carbon Dioxide and Bicarbonate Electroreduction Using a Tetracationic Water-Soluble Cobalt Phthalocyanine.

Electrochemical conversion of carbon dioxide (CO2) offers the opportunity to transform a greenhouse gas into valuable starting materials, chemicals, or fuels. Since many CO2 capture strategies employ aqueous alkaline solutions, there is interest in catalyst systems that can act directly on such capture solutions. Herein, we demonstrate new catalyst designs where the electroactive molecules readily mediate the CO2-to-CO conversion in aqueous solutions between pH 4.5 and 10.5. Likewise, the production of CO directly from 2 M KHCO3 solutions (pH 8.2) is possible. The improved molecular architectures are based on cobalt(II) phthalocyanine and contain four cationic trimethylammonium groups that confer water solubility and contribute to the stabilization of activated intermediates via a concentrated positive charge density around the active core. Turnover frequencies larger than 103 s-1 are possible at catalyst concentrations of down to 250 nM in CO2-saturated solutions. The observed rates are substantially larger than the related cobalt phthalocyanine-containing catalysts. Density functional theory calculations support the idea that the excellent catalytic properties are attributed to the ability of the cationic groups to stabilize CO2-bound reduced intermediates in the catalytic cycle. The homogeneous, aqueous CO2 reduction that these molecules perform opens new frontiers for further development of the CoPc platform and sets a greatly improved baseline for CoPc-mediated CO2 upconversion. Ultimately, this discovery uncovers a strategy for the generation of platforms for practical CO2 reduction catalysts in alkaline solutions.

Metal–Organic Framework Supported Low‐Nuclearity Cluster Catalysts for Highly Selective Carbon Dioxide Electroreduction to Ethanol

AbstractIt is still a great challenge to achieve high selectivity of ethanol in CO2 electroreduction reactions (CO2RR) because of the similar reduction potentials and lower energy barrier of possible other C2+ products. Here, we report a MOF‐based supported low‐nuclearity cluster catalysts (LNCCs), synthesized by electrochemical reduction of three‐dimensional (3D) microporous Cu‐based MOF, that achieves a single‐product Faradaic efficiency (FE) of 82.5 % at −1.0 V (versus the reversible hydrogen electrode) corresponding to the effective current density is 8.66 mA cm−2. By investigating the relationship between the species of reduction products and the types of catalytic sites, it is confirmed that the multi‐site synergism of Cu LNCCs can increase the C−C coupling effect, and thus achieve high FE of CO2–to–ethanol. In addition, density functional theory (DFT) calculation and operando attenuated total reflectance surface‐enhanced infrared absorption spectroscopy further confirmed the reaction path and mechanism of CO2–to–EtOH.

Metal-Organic Framework Supported Low-Nuclearity Cluster Catalysts for Highly Selective Carbon Dioxide Electroreduction to Ethanol.

It is still a great challenge to achieve high selectivity of ethanol in CO2 electroreduction reactions (CO2RR) because of the similar reduction potentials and lower energy barrier of possible other C2+ products. Here, we report a MOF-based supported low-nuclearity cluster catalysts (LNCCs), synthesized by electrochemical reduction of three-dimensional (3D) microporous Cu-based MOF, that achieves a single-product Faradaic efficiency (FE) of 82.5 % at -1.0 V (versus the reversible hydrogen electrode) corresponding to the effective current density is 8.66 mA cm-2. By investigating the relationship between the species of reduction products and the types of catalytic sites, it is confirmed that the multi-site synergism of Cu LNCCs can increase the C-C coupling effect, and thus achieve high FE of CO2-to-ethanol. In addition, density functional theory (DFT) calculation and operando attenuated total reflectance surface-enhanced infrared absorption spectroscopy further confirmed the reaction path and mechanism of CO2-to-EtOH.

Zn-Cu bimetallic gas diffusion electrodes for electrochemical reduction of CO2 to ethylene

The application of renewable energy to drive the electroreduction of carbon dioxide (CO2) into valuable compounds serves as a means of energy storage and simultaneously aids in the mitigation of climate change. In this study, a bimetallic catalyst consisting of Zinc and Copper is synthesized using the Zinc-doped HKUST-1 metal-organic framework. The catalyst is then fabricated on gas diffusional electrode and investigated in both H-Cell and Flow cell configurations for electrochemical CO2 reduction reaction (ECO2RR). In the H-Cell, the catalysts that have been developed exhibit an ethylene faradaic efficiency (FE) up to 40 % when operated at a potential of −0.8 V relative to the reversible hydrogen electrode (RHE). The Zn-Cu bimetallic gas diffusion electrodes (GDE) exhibit an impressive ethylene FE up to 45 % when operating at a current density of −200 mA cm−2 at −1.0 V versus RHE in the flow cell. This research offers valuable insights into the strategic development of copper-based bimetallic catalysts with the aim of enhancing the efficiency of electrochemical reduction of CO2 to yield multicarbon compounds.

Acidic water oxidation with ultralow 131 mV overpotential over surface-reconstructed RuIr nanoalloy: Chloride-driven high performance

The oxygen evolution reaction (OER) in kinetics is sluggish but a key electrode reaction for various energy storage and conversion devices, such as green hydrogen from water electrolysis, rechargeable metal-air battery, sustainable carbon dioxide electroreduction, synthetic ammonia, etc. However, it still remains a major and cutting-edge challenge to pioneering catalysts with simultaneously ultrahigh activity and stability for OER, even with diverse performance enhancement strategies, such as complex composition designs, surface chemical reconstructions, and multiphase engineering have been implemented to accelerate this key electrochemical process. Herein, we proposed a chloride-triggered activation and stabilization strategy for the branched RuIr alloy coated by thin IrO2 layer to achieve unparalleled high-performance toward OER in acidic water. The ultralow overpotential of the activated catalyst is reduced to about 131 mV at 10 mA cm−2, with 79-fold enhancement of mass-activity than commercial IrO2. Moreover, a modified proton exchange membrane water electrolysis (PEMWE) device was first constructed by introducing NaCl into recyclable electrolyte. It run a stably and low cell potential (1.514 V) for 170 h, having no obvious performance decay at 50 mA cm−2 in 0.5 M H2SO4 with 1.6 M NaCl, which far exceeding traditional IrO2||Pt/C PEMWE. The outstanding performance stems from that Cl- ions enable a faster lattice oxygen evolution mechanism. The novel catalyst activates asymmetric O-Ir-Cl structure induced by Cl- filled oxygen vacancies, which modify the electronic and geometric properties, improving OER activity. Moreover, these adsorbed ions can also efficiently patch and refill the oxygen vacancies that ensure the long-term structure stability. Therefore, tailoring the chloride-activated Ir-based catalysts with simultaneously improved activity and stability may be a valuable guide to achieve surprisingly high-performances for acidic water splitting.

Cu-porphyrin-based polymers in electroreduction reactions of gases

In this work, the electrochemical properties of Cu-complexes of di- and tri-amino-substituted tetraphenylporphyrins in dichloromethane were investigated by the cyclic voltammetry method. Electrooxidation of porphyrins in a dichloromethane solution produced polyporphyrin films on the electrode. The formation of polymers occurs through the amino groups of phenyl substituents with the generation of phenazine and dihydrophenazine fragments. The surface morphology and thickness of polyporphyrin films were studied using a scanning electron microscope. The surface of the poly-Cu5,15-di(4′-aminophenyl)-10,20-diphenylporphyrin film is a network of fibers of about 5 µm long and 0.2–0.3 µm thick. The film thickness is 14 µm. The surface of poly-Cu5,10,15-tri(4′-aminophenyl)-20-phenylporphyrin has large branched agglomerates of indefinite shape; the film thickness is 22 µm. The catalytic activity of the obtained polyporphyrin films in oxygen and carbon dioxide electroreduction reactions were evaluated. Poly-Cu5,10,15-tri(4′-aminophenyl)-20-phenylporphyrin was found to be more catalytically active in both reactions, which is evidently associated with a more developed surface of the polymer.

Well-defined asymmetric nitrogen/carbon-coordinated single metal sites for carbon dioxide conversion

Asymmetric nitrogen/carbon-coordinated single metal sites (M-NxC4-x) outperform symmetric M-N4 sites in carbon dioxide (CO2) electroreduction. However, the challenge of crafting well-defined M-NxC4-x sites complicates the understanding of their structure-catalytic performance relationship. In this study, we employ metallized N-confused tetraphenylporphyrin (M-NCTPP) to investigate CO2 conversion on M-N3C1 sites using both density functional theory and experimental methods. The optimal cobalt (Co)-N3C1 site (Co-NCTPP) achieves a current density of 500 mA cm−2 and a carbon monoxide Faraday efficiency exceeding 90 % at −1.25 V vs. the reversible hydrogen electrode, surpassing the performance of Co-N4 (Co-TPP). This research introduces a novel approach for designing and synthesizing high-activity heteroatom-anchored single metal sites, advancing fundamental understanding in the field.