CO2 RR Selectivity Research Articles

Advances in the understanding of selective CO2 reduction catalysis

AbstractThe electrochemical synthesis for value‐added chemicals and fuels via carbon dioxide reduction reaction (CO2RR) offers an effective route to close the anthropogenic carbon cycle and store renewable energy. Currently, the copper‐based catalyst is still the only choice for generating various CO2RR species beyond two electron products. However, the wide range of CO2RR products generated on copper leads to low selectivity, and their low concentrations in electrolytes pose great costs in the downstream purification process and significantly challenge the scalability of this technology. To make this technology economically viable, enhancing product selectivity is crucial. In this review, we identify the primary CO2RR species and discuss the latest insights into the reaction mechanisms controlling CO2RR selectivity. Then, we examined factors that affect CO2RR selectivity. Emphasizing these factors in catalyst design, we highlight the importance of advanced technologies to expand our knowledge and prospects for the future of the CO2RR.

Asymmetrically Coordinated Cu Dual-Atom-Sites Enables Selective CO2 Electroreduction to Ethanol.

Electrochemical reduction of CO2 (CO2RR) to value-added liquid fuels is a highly attractive solution for carbon-neutral recycling, especially for C2+ products. However, the selectivity control to preferable products is a great challenge due to the complex multi-electron proton transfer process. In this work, a series of Cu atomic dispersed catalysts are synthesized by regulating the coordination structures to optimize the CO2RR selectivity. Cu2-SNC catalyst with a uniquely asymmetrical coordinated CuN2-CuNS site shows high ethanol selective with the FE of 62.6% at -0.8V versus RHE and 60.2% at 0.9V versus RHE in H-Cell and Flow-Cell test, respectively. Besides, the nest-like structure of Cu2-SNC is beneficial to the mass transfer process and the selection of catalytic products. In situ experiments and theory calculations reveal the reaction mechanisms of such high selectivity of ethanol. The S atoms weaken the bonding ability of the adjacent Cu to the carbon atom, which accelerates the selection from *CHCOH to generate *CHCHOH, resulting in the high selectivity of ethanol. This work indicates a promising strategy in the rational design of asymmetrically coordinated single, dual, or tri-atom catalysts and provides a candidate material for CO2RR to produce ethanol.

Biomimetic Phthalocyanine‐Based Covalent Organic Frameworks with Tunable Pendant Groups for Electrocatalytic CO2 Reduction

AbstractElectrocatalytic carbon dioxide reduction reaction (CO2RR) is an effective way of converting CO2 into value‐added products using renewable energy, whose activity and selectivity can be in principle maneuvered by tuning the microenvironment near catalytic sites. Here, we demonstrate a strategy for tuning the microenvironment of CO2RR by learning from the natural chlorophyll and heme. Specifically, the conductive covalent organic frameworks (COFs) linked by piperazine serve as versatile supports for single‐atom catalysts (SACs), and the pendant groups modified on the COFs can be readily tailored to offer different push‐pull electronic effects for tunable microenvironment. As a result, while all the COFs exhibit high chemical structure stability under harsh conditions and good conductivity, the addition of −CH2NH2 can greatly enhance the activity and selectivity of CO2RR. As proven by experimental characterization and theoretical simulation, the electron‐donating group (−CH2NH2) not only reduces the surface work function of COF, but also improves the adsorption energy of the key intermediate *COOH, compared with the COFs with electron‐withdrawing groups (−CN, −COOH) near the active sites. This work provides insights into the microenvironment modulation of CO2RR electrocatalysts at the molecular level.

Biomimetic Phthalocyanine-Based Covalent Organic Frameworks with Tunable Pendant Groups for Electrocatalytic CO2 Reduction.

Electrocatalytic carbon dioxide reduction reaction (CO2RR) is an effective way of converting CO2 into value-added products using renewable energy, whose activity and selectivity can be in principle maneuvered by tuning the microenvironment near catalytic sites. Here, we demonstrate a strategy for tuning the microenvironment of CO2RR by learning from the natural chlorophyll and heme. Specifically, the conductive covalent organic frameworks (COFs) linked by piperazine serve as versatile supports for single-atom catalysts (SACs), and the pendant groups modified on the COFs can be readily tailored to offer different push-pull electronic effects for tunable microenvironment. As a result, while all the COFs exhibit high chemical structure stability under harsh conditions and good conductivity, the addition of -CH2NH2 can greatly enhance the activity and selectivity of CO2RR. As proven by experimental characterization and theoretical simulation, the electron-donating group (-CH2NH2) not only reduces the surface work function of COF, but also improves the adsorption energy of the key intermediate *COOH, compared with the COFs with electron-withdrawing groups (-CN, -COOH) near the active sites. This work provides insights into the microenvironment modulation of CO2RR electrocatalysts at the molecular level.

Selective CO2 Reduction over γ-Graphyne Supported Single-Atom Catalysts: Crucial Role of Strain Regulation.

The two-electron CO2 reduction reaction (2e-CO2RR) is the most promising process for realizing industrial utilization of CO2, but it is hindered by the competitive hydrogen evolution reaction (HER) because of the comparable equilibrium potential. Strategies to enhance 2e-CO2RR activity and selectivity by suppressing HER are highly demanded. Inspired by the low in-plane Young's modulus of the recently synthesized γ-graphyne (GY), we propose tensile-strain regulation as an effective method to improve the selectivity of the CO2RR against HER. By means of constant-potential calculations and constrained ab initio molecular dynamics simulations, we demonstrate the good stability and high CO2RR activity of GY-supported Co (Co-GY) single-atom catalysts (SACs). The change in potential of zero charges of *COOH is revealed to be more sensitive to tensile strain than that of *H species on Co-GY SACs, resulting in a slower change of its adsorption energy than that of *H species under working potentials and consequently enhanced CO2RR selectivity toward CO production. Besides, the strain-dependent regulation mechanism also applies to other M-GY SACs, demonstrating strain regulation as an effective strategy for designing and manipulating SACs for the selective 2e-CO2RR.

Key Factors for Electrochemical Carbon Dioxide Reduction at Ni-N-C Catalysts

Electrochemical carbon dioxide reduction reaction (CO2RR) has the potential to adequately contribute to addressing the energy and environmental challenges faced by the humanity today. The surplus of CO2 produced by burning fossil fuels can be transformed into valuable products by CO2RR. An effective use of this approach on a large scale requires active, selective, and stable CO2 reduction electrocatalysts. Additionally, insightful understanding of interfacial behavior such as water wetting and carbonate formation at the electrode is required to enhance the performance and durability of CO2RR electrocatalysts.1 Atomically dispersed Ni-N-C materials have attracted attention due to their superior selectivity for CO generation.2 Their activity and selectivity of CO2RR are influenced by the metal center and local atomic defects in M-N-C catalysts.3 In addition to catalyst structures, electrode composition and structure have also substantial impact on the activity and selectivity of CO2RR. Particularly, ionomer compositions and the electrode fabrication process can alter the hydrophobicity of the electrode and the local pH on the catalyst, resulting in considerable changes in CO2RR activity and selectivity.In this presentation, we will report on the performance of various electrodes fabricated with the Ni-N-C catalyst, using different types of ionomers and measured in a flow cell and zero-gap electrolyzer at > 100 mA/cm2 current densities for CO2RR. We will also introduce an approach that aims at reducing carbonate formation at the CO2RR electrolyzer cathode by the modifications to the electrolyte composition, the CO2 inlet humidity, and the electrochemical cell temperature. Acknowledgement Research presented in this work was supported by the Laboratory Directed Research and Development program of Los Alamos National Laboratory under project number 20230065DR. References (1) Sa, Y. J.; Lee, C. W.; Lee, S. Y.; Na, J.; Lee, U.; Hwang, Y. J. Catalyst–electrolyte interface chemistry for electrochemical CO2 reduction. Chemical Society Reviews 2020, 49 (18), 6632-6665.(2) Wu, J.; Sharifi, T.; Gao, Y.; Zhang, T.; Ajayan, P. M. Emerging Carbon-Based Heterogeneous Catalysts for Electrochemical Reduction of Carbon Dioxide into Value-Added Chemicals. Advanced Materials 2019, 31 (13), 1804257.(3) Liang, S.; Huang, L.; Gao, Y.; Wang, Q.; Liu, B. Electrochemical Reduction of CO2 to CO over Transition Metal/N-Doped Carbon Catalysts: The Active Sites and Reaction Mechanism. Advanced Science 2021, 8 (24), 2102886.

Local-strain-induced CO2 adsorption geometries and electrochemical reduction pathway shift.

Unravelling the influence of strain and geometric effects on the electrochemical reduction of carbon dioxide (CO2RR) on Cu-based (or Pd-based) alloys remains challenging due to complex local microenvironment variables. Herein, we employ two PdCu alloys (nanoparticles and nanodendrites) to demonstrate how CO2RR selectivity can shift from CO to HCOO-. Despite sharing consistent phases, exposed crystal facets, and overall oxidative states, these alloys exhibit different local strain profiles due to their distinct geometries. By integrating experimental data, in-situ spectroscopy, and density functional theory calculations, we revealed that CO2 prefers adsorption on tensile-strained areas with carbon-side geometry, following a *COOH-to-CO pathway. Conversely, on some compressive-strained regions induced by the dendrite-like morphology, CO2 adopts an oxygen-side geometry, favoring an *OCHO-to-HCOO pathway due to the downshift of the d-band center. Notably, our findings elucidate a dominant *OCHO-to-HCOO- pathway in catalysts when featuring both adsorption geometries. This research provides a comprehensive model for local environment of bimetallic alloys, and establishes a clear relationship between the CO2RR pathway shift and variation in local strain environments of PdCu alloys.

Efficient tuning of the selectivity of Cu-based interface for electrocatalytic CO2 reduction by ligand modification

The development of efficient strategies to tune the CO2RR selectivity of Cu-based catalytic interfaces, especially on specific domains, such as Cu (200) facets with high activity toward competitive hydrogenation evolution reaction (HER), remains a challenging task. In this work, Cu-based catalytic layers with thiocyanate (-SCN), cyanide (-CN), or ethylenediamine (-NH2R) coordination linkages are prepared on Cu nanocolumns arrays (Cu NCAs) with predominant (200) exposed facets. The coordination of these ligands induces more Cu+ species and inhibits the adsorption of H∗ on the Cu (200) facet, leading to enhanced CO2RR performance and substantially suppressing the competitive HER. The faradaic efficiency (FE) of Cu–SCN, Cu–CN, and Cu–NH2R NWAs for producing HCOOH, C2H4, and C1 mixture products (HCOOH and CO) reach to 66.5%, 21.1%, and 57.1%, respectively. In situ spectroscopic studies reveal Cu–SCN, Cu–CN, and Cu–NH2R exhibit more reasonable adsorption energy toward ∗OCHO, ∗CO, and ∗COOH intermediates, promoting the HCOOH, C2H4, and C1 mixture generation, respectively. This study might provide a new perspective for the development of high-performance Cu-based CO2RR catalytic electrodes based on the combination of various commercial free-standing Cu substrates and organic/inorganic ligands.

Density Functional Study of Electrocatalytic Carbon Dioxide Reduction in Fourth-Period Transition Metal-Tetrahydroxyquinone Organic Framework.

This study investigates the utilisation of organometallic network frameworks composed of fourth-period transition metals and tetrahydroxyquinone (THQ) in electrocatalytic CO2 reduction. Density functional theory (DFT) calculations were employed in analysing binding energies, as well as the stabilities of metal atoms within the THQ frameworks, for transition metal TM-THQs ranging from Y to Cd. The findings demonstrate how metal atoms could be effectively dispersed and held within the THQ frameworks due to sufficiently high binding energies. Most TM-THQ frameworks exhibited favourable selectivity towards CO2 reduction, except for Tc and Ru, which experienced competition from hydrogen evolution reaction (HER) and required solution environments with pH values greater than 5.716 and 8.819, respectively, to exhibit CO2RR selectivity. Notably, the primary product of Y, Ag, and Cd was HCOOH; Mo produced HCHO; Pd yielded CO; and Zr, Nb, Tc, Ru, and Rh predominantly generated CH4. Among the studied frameworks, Zr-THQ displayed values of 1.212 V and 1.043 V, corresponding to the highest limiting potential and overpotential, respectively, while other metal-organic frameworks displayed relatively low ranges of overpotentials from 0.179 V to 0.949 V. Consequently, it is predicted that the TM-THQ framework constructed using a fourth-period transition metal and tetrahydroxyquinone exhibits robust electrocatalytic reduction of CO2 catalytic activity.

Accelerating the Reaction Kinetics of CO2 Reduction to Multi-Carbon Products by Synergistic Effect between Cation and Aprotic Solvent on Copper Electrodes.

Improving the selectivity of electrochemical CO2 reduction to multi-carbon products (C2+ ) is an important and highly challenging topic. In this work, we propose and validate an effective strategy to improve C2+ selectivity on Cu electrodes, by introducing a synergistic effect between cation (Na+ ) and aprotic solvent (DMSO) to the electrolyte. Based on constant potential ab initio molecular dynamics simulations, we first revealed that Na+ facilitates C-C coupling while inhibits CH3 OH/CH4 products via reducing the water network connectivity near the electrode. Furthermore, the water network connectivity was further decreased by introducing an aprotic solvent DMSO, leading to suppression of both C1 production and hydrogen evolution reaction with minimal effect on *OCCO* hydrogenation. The synergistic effect enhancing C2 selectivity was also experimentally verified through electrochemical measurements. The results showed that the Faradaic efficiency of C2 increases from 9.3 % to 57 % at 50 mA/cm2 under a mixed electrolyte of NaHCO3 and DMSO compared to a pure NaHCO3 , which can significantly enhance the selectivity of the C2 product. Therefore, our discovery provides an effective electrolyte-based strategy for tuning CO2 RR selectivity through modulating the microenvironment at the electrode-electrolyte interface.

Accelerating the Reaction Kinetics of CO2 Reduction to Multi‐Carbon Products by Synergistic Effect between Cation and Aprotic Solvent on Copper Electrodes

AbstractImproving the selectivity of electrochemical CO2 reduction to multi‐carbon products (C2+) is an important and highly challenging topic. In this work, we propose and validate an effective strategy to improve C2+ selectivity on Cu electrodes, by introducing a synergistic effect between cation (Na+) and aprotic solvent (DMSO) to the electrolyte. Based on constant potential ab initio molecular dynamics simulations, we first revealed that Na+ facilitates C−C coupling while inhibits CH3OH/CH4 products via reducing the water network connectivity near the electrode. Furthermore, the water network connectivity was further decreased by introducing an aprotic solvent DMSO, leading to suppression of both C1 production and hydrogen evolution reaction with minimal effect on *OCCO* hydrogenation. The synergistic effect enhancing C2 selectivity was also experimentally verified through electrochemical measurements. The results showed that the Faradaic efficiency of C2 increases from 9.3 % to 57 % at 50 mA/cm2 under a mixed electrolyte of NaHCO3 and DMSO compared to a pure NaHCO3, which can significantly enhance the selectivity of the C2 product. Therefore, our discovery provides an effective electrolyte‐based strategy for tuning CO2RR selectivity through modulating the microenvironment at the electrode‐electrolyte interface.

Molecular understanding of the critical role of alkali metal cations in initiating CO2 electroreduction on Cu(100) surface

Molecular understanding of the solid–liquid interface is challenging but essential to elucidate the role of the environment on the kinetics of electrochemical reactions. Alkali metal cations (M+), as a vital component at the interface, are found to be necessary for the initiation of carbon dioxide reduction reaction (CO2RR) on coinage metals, and the activity and selectivity of CO2RR could be further enhanced with the cation changing from Li+ to Cs+, while the underlying mechanisms are not well understood. Herein, using ab initio molecular dynamics simulations with explicit solvation and enhanced sampling methods, we systematically investigate the role of M+ in CO2RR on Cu surface. A monotonically decreasing CO2 activation barrier is obtained from Li+ to Cs+, which is attributed to the different coordination abilities of M+ with *CO2. Furthermore, we show that the competing hydrogen evolution reaction must be considered simultaneously to understand the crucial role of alkali metal cations in CO2RR on Cu surfaces, where H+ is repelled from the interface and constrained by M+. Our results provide significant insights into the design of electrochemical environments and highlight the importance of explicitly including the solvation and competing reactions in theoretical simulations of CO2RR.

Facilely tunable dodecahedral polyoxometalate framework loaded with mono- or bimetallic sites for efficient photocatalytic CO2 reduction

Utilizing solar energy to drive the conversion of CO2 into high-value chemicals emerged as a promising approach to decrease CO2 emission. Yolk-shell or hollow structure have drawn much attention for photocatalytic CO2 reduction, owing to their efficient CO2 trapping and more active sites exposing. In this study, we employed a simple method to regulate the morphological evolution of K3PW12O40 dodecahedra. After annealing, mono-/bimetallic active species are homogeneously dispersed on K3PW12O40 framework forming PW12 @Co and PW12 @CoNi, which exhibit good CO production rates of 11.2 and 15.1 μmol/h, respectively, with selectivity of 90.7% and 92.6%. The differences in the activity and selectivity of CO2RR are attributed to the morphology variations of POM and the influence of mono-/bimetallic species. These results are confirmed through the analysis of SEM, TEM, N2 and CO2 adsorption/desorption, PL, EIS and SPV characterizations. In-situ DRIFTS and DFT provide further support for the formation and transformation of intermediate products.

Screening of Transition Metal Supported on Black Phosphorus as Electrocatalysts for CO2 Reduction.

The electrocatalytic CO2 reduction (CO2RR) is an effective and economical strategy to eliminate CO2 through conversion into value-added chemicals and fuels. However, exploring and screening suitable 2D material-based single-atom catalysts (SACs) for CO2 reduction are still a great challenge. In this study, 27 (3d, 4d, and 5d, except Tc and Hg) transition metal (TM) atom-doped black phosphorus (TM@BP) electrocatalysts were systematically investigated for CO2RR by density functional theory calculations. According to the stability of SACs and their effectiveness in activating the CO2 molecule, three promising catalysts, Zr@BP, Nb@BP, and Ru@BP, were successfully screened out, exhibiting outstanding catalytic activity for the production of carbon monoxide (CO), methyl alcohol (CH3OH), and methane (CH4) with limiting potentials of -0.79, -0.49, and -0.60 V, respectively. A catalytic relationship between the d-band centers of SACs and the limiting potential of CO2RR was used to estimate the catalytic activity of catalysts. Furthermore, Nb@BP has high selectivity for CO2RR to CH3OH compared to H2 formation, while the hydrogen evolution reaction significantly impacts the synthesis of CO and CH4 on Zr@BP and Ru@BP. Nitrogen atom doping in BP is beneficial for enhancing the selectivity of CO2RR, but it is detrimental to the activity of CO2RR. This study offers theoretical guidance for synthesizing highly efficient CO2RR electrocatalysts and further enhances structural modulation methods for layered 2D materials.

Effects of the delocalization state on electrocatalytic CO2 reduction: a mini-review

The delocalization state of catalysts has been found to promote the stability and selectivity of CO2RR. This mini-review was discussed how the delocalization state of catalysts affects catalytic properties.

Experimental trends and theoretical descriptors for electrochemical reduction of carbon dioxide to formate over Sn-based bimetallic catalysts

Understanding CO2RR selectivity of Sn-based catalysts by considering both the real-time structural evolution of catalysts and all key intermediates involved.

Efficient mapping of CO adsorption on Cu1−xMx bimetallic alloys via machine learning

A two-step machine learning model to predict CO binding energies on CuM(111)/(100) bimetallic surfaces and enhance the CO2RR selectivity towards C2 products.

Modulating the Product Distribution of the Electrochemical Reduction of CO2 on Copper at Relevant Current Densities

The electrochemical reduction of CO2 (CO2RR) has the potential to be an economically-viable method to produce platform chemicals synergistically with renewable energy sources. Copper is one of the most used electro-catalysts for this purpose, as it allows carbon-carbon bond formation, crucial for broader product distribution. Despite great achievements, controlling selectivity is yet a stepping stone between R&D and an actual industrial application. Among others, a kinetic resolution could be applied to enhance the selectivity toward targeted products, for which exploiting available and inexpensive additives or co-electrolytes such as ionic liquids is a promising direction. Herein, we present an initial systematic analysis of the effect of various tetra alkyl ammonium salts on the CO2RR products distribution with the aim on ethylene, important industrial feedstock or building block. A selected ammonium salts of different alkyl chain length and number of charges provided very concise but sufficient chemical space to overview a structure-activity relationships, including changes in the reactions’ onset potentials and limiting currents. The overall experimentation progress was intensified by the employing a developed in our lab a gas diffusion electrode (GDE) cell, coupled to a mass spectrometer. This enabled to scan the selected library of salts during CO2RR under dynamic operations with detection of transients in real-time at relatively high current densities, between 10 to 400 mA/cm2, within further quantitative validation over standard long-term steady-state experiments. These results have broad implications for effectively stirring the CO2RR selectivity towards products containing either one or two carbon atoms.Key words: CO2, Electroreduction, Copper, Electrocatalysis, Modifiers, Real-time, GDE

A Molecular Copper Catalyst for Electrochemical Conversion of CO2 to C2+ Products

Electrochemical carbon dioxide reduction (CO2RR) is a promising route to address the excessive emission of CO2 and the depletion of fossil fuels.[1] Metallic Cu and Cu-based materials have attracted increased attention, as Cu is the only metal that can reliably convert CO2 into hydrocarbons and oxygenates, such as ethanol, ethylene, and n-propanol.[2] To optimize CO2-to-C2+ conversion, considerable efforts were made to modify the catalyst composition and structure, adjusting the electrolyte, and optimizing the electrochemical setup.[3] In this context, molecular catalysts (i.e. transition metal complexes) are interesting alternatives, since the performance can be precisely tuned via ligand modification and due to the possibility for mechanistic studies at well-defined and uniform active sites.[4]Herein, a catalytic system based on an immobilized dinuclear Cu phenanthroline complex is reported that can be prepared with a straightforward synthetic method. The catalyst exhibits excellent CO2RR selectivity toward C-C coupling in aqueous electrolytes with only small production of H2. The highest Faradaic efficiency (FE) for C2+ products achieved was 62% at -1.85 V vs. Ag/AgCl with less than 10% FE for H2. Furthermore, a steady current density and a stable FE(C2H4) over 10 h continuous operation indicate a good stability of the Cu complex. In this contribution, both the electrolysis results and the relationship between structural aspects and product selectivity will be discussed, the latter based on scanning/transmission electron microscopy, X-ray photoelectron/absorption spectroscopy, and further analytical techniques.Literature:[1] X. Su, Z. Jiang, J. Zhou, H. Liu, D. Zhou, H. Shang, X. Ni, Z. Peng, F. Yang, W. Chen, Z. Qi, D. Wang, Y. Wang, Nat. Commun. 2022, 13, 1322. [2] W. Quan, Y. Lin, Y. Luo, Y. Huang, Adv. Sci. 2021, 8, e2101597. [3] J. Yu, J. Wang, Y. Ma, J. Zhou, Y. Wang, P. Lu, J. Yin, R. Ye, Z. Zhu, Z. Fan, Adv. Funct. Mater. 2021, 31. [4] D. H. Nam, P. De Luna, A. Rosas-Hernandez, A. Thevenon, F. Li, T. Agapie, J. C. Peters, O. Shekhah, M. Eddaoudi, E. H. Sargent, Nat. Mater. 2020, 19, 266.

Unveiled the Structure-Selectivity Relationship for Carbon Dioxide Reduction Triggered by Bi-Doped Cu-Based Nanocatalysts.

To investigate synergistic effect between geometric and electronic structures on directing CO2RR selectivity, water phase synthetic protocol and surface architecture engineering strategy are developed to construct monodispersed Bi-doped Cu-based nanocatalysts. The strongly correlated catalytic directionality and Bi3+ dopant can be rationalized by the regulation of [*COOH]/[*CO] adsorption capacities through the appropriate doping of Bi3+ electronic modulator, resulting in volcano relationship between FECO/TOFCO and surface EVBM values. Spectroscopic study reveals that the dual-site binding mode ([Cu─μ─C(═O)O─Bi3+]) enabled by Cu1Bi3+ 2 motif in single-phase Cu150Bi1 nanocatalyst drives CO2-to-CO conversion. In contrast, the study of dynamic Bi speciation and phase transformation in dual-phase Cu50Bi1 nanocatalyst unveils that the Bi0-Bi0 contribution emerges at the expense of BOC phase, suggesting metallic Bi0 phase acting as [H]˙ formation center switches CO2RR selectivity toward CO2-to-HCOO- conversion via [*OCHO] and [*OCHOK] intermediates. This work provides significant insight into how geometric architecture cooperates with electronic effect and catalytic motif/phase to guide the selectivity of electrocatalytic CO2 reduction through the distinct surface-bound intermediates and presents molecular-level understanding of catalytic mechanism for CO/HCOO- formation.