Perovskite Cathode Research Articles

Na+ doping activates and stabilizes layered perovskite cathodes for high-performance fuel cells

A highly active mixed conductive cathode is required for solid oxide fuel cells (SOFCs) based on yttria-stabilized zirconia (YSZ) at reduced temperatures, which is one of the most important factors for their commercialization. Herein, we propose a Na+ doping strategy to activate and stabilize the triple-conducting (H+/O2−/e−) layered perovskite oxide of representative NdBa0.5Sr0.5Co1.5Fe0.5O5+δ (NBSCF) for high-performance YSZ fuel cells. The results show that Na+ doping enhances the electrochemical properties of the NBSCF cathode, with polarization impedance decreasing from 0.105 to 0.080 Ω cm2 at 750 °C and output power increasing from 946.05 to 1435.75 mW cm−2 at 800 °C. Furthermore, high-temperature XRD (HT-XRD) and the oxygen temperature-programmed desorption (O2-TPD) further confirm that Na+ doping can improve the structural stability of NBSCF. The single cell with a Na-doped NBSCF cathode showed no degradation of current density for more than 120 h at 700 °C and exhibited good stability. This work demonstrates the promise of Na+ doping for layered perovskite cathodes and an effective way to promote fuel cell performance.

Visiting the roles of Sr‐ or Ca‐ doping on the oxygen reduction reaction activity and stability of a perovskite cathode for proton conducting solid oxide fuel cells

AbstractWhile double perovskites of PrBaCo2O6 (PBC) have been extensively developed as the cathodes for proton‐conducting solid oxide fuel cells (H‐SOFCs), the effects of Sr‐ or Ca‐doping at the A site on the activity and stability of the oxygen reduction reaction are yet to be fully studied. Here, the effect of A‐site doping on the oxygen reduction reaction activity and stability has been studied by evaluating the performance of both symmetrical and single cells. It is shown that Ca‐doped PBC (PrBa0.8Ca0.2Co2O6, PBCC) shows a slightly smaller polarization resistance (0.076 Ω cm2) than that (0.085 Ω cm2) of Sr‐doped PBC (PrBa0.8Sr0.2Co2O6, PBSC) at 700°C in wet air. Moreover, the degradation rate of PBCC is 0.0003 Ω cm2 h−1 (0.3% h−1) in 100 h, about 1/10 of that of PBSC at 700°C in wet air. In addition, it is also confirmed that single cells with PBCC cathode show higher peak power density (1.22 W cm−2 vs. 1.08 W cm−2 at 650°C) and better durability (degradation rate of 0.1% h−1 vs. 0.13% h−1) than those with PBSC cathode. The distribution of relaxation time analyses suggests that the better stability of the PBCC electrode may come from the fast and stable surface oxygen exchange process in the medium frequency range of the electrochemical impedance spectrum.

In situ passivation of Fe nanoparticles exsolved from perovskite cathodes through zinc doping for CO2 electrolysis

In-situ passivation of Fe nanoparticles exsolved from perovskite cathodes for improving catalytic activity of CO2 electrolysis.

Exploring the potential of triple conducting perovskite cathodes for high-performance solid oxide fuel cells: a comprehensive review

We report many factors that affect the uptake and conduction of ions of triple conducting perovskites (TCPs) and the current research progress of TCPs by dividing TCPs into three categories.

Enhanced Compatibility and Activity of High-entropy Double Perovskite Cathode Material for IT-SOFC

Enhanced Compatibility and Activity of High-entropy Double Perovskite Cathode Material for IT-SOFC

Enhancing catalytic activity of CO2 electrolysis via B-site cation doped perovskite cathode in solid oxide electrolysis cell

Solid oxide electrolysis cell (SOEC) is considered as a high energy-efficient CO2 conversion method and a promising technology to achieve carbon neutralization. Thus, in this work, the reduced Co or Ni doped Pr0.4Sr0.6Fe0.9Mo0.1O3 perovskite oxides are used as the cathode of SOEC. After reduction, Co-Fe alloy nanoparticles are in situ exsolved from Pr0.4Sr0.6Co0.2Fe0.7Mo0.1O3 and Pr0.4Sr0.6Co0.45Fe0.45Mo0.1O3, and NiFe10.8 alloy nanoparticles are attached on the Pr0.4Sr0.6Ni0.2Fe0.7Mo0.1O3 matrix. The reduced Pr0.4Sr0.6Ni0.2Fe0.7Mo0.1O3 exhibits the highest oxygen vacancy concentration and CO2 adsorption ability, which further promote oxygen surface exchange and electrochemical surface exchange reaction. Besides, the reduced Pr0.4Sr0.6Ni0.2Fe0.7Mo0.1O3 exhibits the highest surface reaction rate constant (kchem) of 3.54 × 10-4 cm s-1 and highest oxygen chemical bulk diffusion coefficient (Dchem) of 27.53 × 10-5 cm2 s-1, suggesting that reduced Pr0.4Sr0.6Ni0.2Fe0.7Mo0.1O3 shows the best catalytic activity for CO2 reduction reaction. The symmetrical cell with reduced Pr0.4Sr0.6Ni0.2Fe0.7Mo0.1O3 shows the lowest polarization resistance (Rp) value, and at 800 °C, the electrolysis cell with reduced Pr0.4Sr0.6Ni0.2Fe0.7Mo0.1O3 cathode also exhibits the best performance of 0.81 A cm-2 in 50%CO-50%CO2 and 1.05 A cm-2 in pure CO2 at 1.5 V, indicating that reduced Pr0.4Sr0.6Ni0.2Fe0.7Mo0.1O3 is a promising cathode for CO2 electrolysis.

Enhanced Electrolysis of CO2 with Metal–Oxide Interfaces in Perovskite Cathode in Solid Oxide Electrolysis Cell

The application of solid oxide electrolysis cell in CO2 electroreduction is a hot research topic at present, but the development of low−cost catalysts with high catalytic activity has always been a challenge for this work. Herein, we use NiCu alloy nanoparticles to modify the perovskite LSCM electrode to build a metal–oxide active interface to obtain high catalytic performance. At 850 °C, 4.66 mL min−1 cm−2 CO productivity and 97.7% Faraday current efficiency were obtained. In addition, the current remained stable during the 100 h long−term test, indicating that the active interface has the dual effect of improving catalytic performance and maintaining cell durability.

The substitution of La and Ba in X0.5Sr0.5Co0.8Mn0.2O3 as a perovskite cathode for low temperature solid oxide fuel cells

Here we report the synthesis of La and Ba substituted X0.5Sr0.5Co0.8Mn0.2O3 using sol–gel auto-combustion method and their investigation as a low temperature solid oxide fuel cell. Structural investigations revealed that La0.5Sr0.5Co0.8Mn0.2O3 (LSCM) crystallized out in rhombohedral perovskite structure while Ba0.5Sr0.5Co0.8Mn0.2O3 (BSCM) has hexagonal perovskite structure. Morphological analysis confirmed the porous structure with uniform distribution of grains. However, agglomeration is decreased when La is replaced with Ba. The existence of all constituent elements as per their stochiometric ratio is evaluated through energy dispersive X-ray spectroscopy. Maximum conductivity value obtained at 600 °C for LSCM and BSCM is 3.51 Scm−1 and 2.26 Scm−1, respectively. In addition, the maximum values of current density and power density achieved by LSCM are 808 mAcm−2 and 277 mWcm−2 while that of BSCM are 663 mAcm−2 and 186 mWcm−2, respectively at low operating temperature of 600 °C. Furthermore, the open circuit voltage (VOC) of LSCM and BSCM based fuel cells is 0.87 V and 0.72 V, respectively which indicates that there are minimal activation losses in the cells. These results showed that the fuel cell based on LSCM cathode has significantly higher values of power density and VOC than that of BSCM based fuel cell. Therefore, LSCM based fuel cell are potential candidate for low temperature futuristic solid-state devices.

High-performance proton ceramic fuel cells using a perovskite oxide cathode surface decorated with CoOx nanoparticles

This study reports on the performance improvement of a protonic ceramic fuel cell (PCFC) after a CoOx nanoparticle treatment has been applied to a PrBa0.5Sr0.5Co2-xFexO5+δ(PBSCF) cathode with a perovskite structure. CoOx nanoparticles are deposited on the sintered PBSCF surface using a plasma-enhanced (PE) atomic layer deposition (ALD) process, thereby avoiding any unwanted reactions or phase changes. The CoOx nanoparticles are successfully deposited uniformly onto the entire surface of the porous and complex cathode structure. A constant deposition rate is observed because of the self-limiting characteristics of the ALD process by a thickness difference as a function of a change in the cycle count. In our experiment, the performance of the fuel cells increases by approximately 36 % compared with the untreated cells at an operating temperature of 650 °C. In addition, all cells feature long-term stability. Impedance analysis reveals that the CoOx nanoparticle treatment results in a significant polarization and some ohmic loss improvement within all temperature regions. This is due to the synergistic effect with PBSCF and self-catalytic effects. The results imply that the proposed method enables high-performance PCFC fabrication; additionally it helps lowering the operating temperature.

The promoting effect of Sr-doping on the oxygen reduction activity of perovskite cathode

A stable cathode with high catalytic activity toward oxygen reduction reaction (ORR) plays a key role in the commercialization of solid oxide fuel cells (SOFCs). The cathode material Ba0.8Sr0.2Co0.7Fe0.2Nb0.1O3-δ is synthesized by solid-state reaction method. The introduction of Sr result in a higher porosity and a lower thermal expansion coefficient. It optimizes the concentration ratio of small polarons and oxygen vacancies. The overall reaction of Ba0.8Sr0.2Co0.7Fe0.2Nb0.1O3-δ cathode is determined by three main ORR processes. The change in rate-limiting step are related to partial pressure of oxygen. The ionization process of oxygen atoms is the main rate-limiting step when PO2 is higher than 0.01 atm. The addition of Sr2+ accelerates the ionization process of oxygen atoms and leads to the acceleration of the whole ORR process. The temperature mainly affects the oxygen transport on the cathode surface and in the cathode bulk. The transfer of oxygen ions to the electrolyte and the ionization of oxygen atoms are accelerated at high temperatures.

High-entropy approach to double perovskite cathode materials for solid oxide fuel cells: Is multicomponent occupancy in (La,Pr,Nd,Sm,Gd)BaCo2O5+δ affecting physicochemical and electrocatalytic properties?

High-entropy (La,Pr,Nd,Sm,Gd)BaCo2O5+δ double perovskite-type oxide having an equimolar, high-entropy, A-site-layered arrangement of cations is synthesized for the first time. A modified Pechini method, followed by calcination and sintering at 1,100°C helps in obtaining a single-phase, homogenous material with tetragonal I4/mmm symmetry. In situ X-ray diffraction and dilatometric studies show excellent phase stability up to 1,100°C in air, with the average thermal expansion coefficient of 23.7∙10–6 K−1 within the 25–1,100°C range. Total electrical conductivity of the metallic character exceeds 1,600 S cm−1 at room temperature. Equilibrated oxygen content at room temperature is determined as 5.69. The cathodic polarization resistance of the (La,Pr,Nd,Sm,Gd)BaCo2O5+δ layers, manufactured on the La0.8Sr0.2Ga0.8Mg0.2O2.8 (LSGM) solid electrolyte of proved inertness, is as low as 0.037 Ω cm2 at 900°C, and 0.175 Ω cm2 at 750°C. The determined value of the power density in the LSGM-based, electrolyte-supported (thickness ca. 200 μm) fuel cell reaches 857 mW cm−2. These results indicate possible applicability of the developed cathode material for solid oxide fuel cells, making it also one of the best-performing high-entropy air electrodes reported until now. However, the determined physiochemical characteristics of the material indicate a relatively limited influence of the high-entropy A-site arrangement in comparison to the conventional analogs, including the synthesized Nd0.88Sm0.12Co2O5+δ composition, characterized by the same effective radius of the lanthanide cations.

Synthesis of ammonia from water and nitrogen using a compo-site cathode based on La0.6Ba0.4Fe0.8Cu0.2O3-δ-Ce0.8Gd0.18Ca0.02O2-δ

Carbon-free electrochemical synthesis of ammonia is a promising technology for CO2 emission reduction. This study aims to explore the electrocatalytic activity of A-site Ba-doped perovskite cathode catalyst (La0.6Ba0.4Fe0.8Cu0.2O3-δ, LBFCu) for ammonia synthesis from water and nitrogen. LBFCu was prepared via the sol-gel method using combined EDTA-citrate complexing agents and characterized by X-ray diffraction (XRD) and scanning electron microscope (SEM). Ammonia was successfully synthesised from water and nitrogen under atmospheric pressure, and LBFCu mixed with Ce0.8Gd0.18Ca0.02O2-δ (CGDC) was used as a cathode. When a voltage was applied to the cell containing CGDC-carbonate composite solid electrolyte, ammonia formation was observed at 375, 400, 425 and 450 °C. At 400 °C and 1.4 V, the maximum rate of ammonia production was achieved at 4.0×10-11 mol s-1 cm-2, which corresponds to Faradaic efficiency of ~ 0.06 % at the current density of 19 mA cm-2. According to the findings, the synthesis of ammonia directly from water and nitrogen may be considered a promising green synthesis technology.

Novel CO2-tolerant Co-based double perovskite cathode for intermediate temperature solid oxide fuel cells

For the commercial application of solid oxide fuel cells (SOFCs), CO2-tolerant cathode materials with high electrochemical activity are required. Here, we discuss the performance of double perovskite Pr0.2Sr1.8CoTiO6−δ (P02STC) as a potential cathode material for SOFCs. P02STC has a cubic structure and keeps lattice structure stable in the CO2 atmosphere. The average thermal expansion coefficient is 17.8 × 10–6 K–1 at 30–900 °C in air. The P02STC cathode exhibits good electrochemical performance with a low polarization resistance of 0.080 Ωcm2 at 700 °C. The P02STC cathode shows good structure stability, electrochemical performance stability, and excellent tolerance to CO2 poisoning for the symmetrical cells based on the 350 h stability test in air and the 150 h stability test in O2 containing 5%CO2 at 700 °C. The electrolyte-supported single cell with a P02STC cathode shows a maximum power density of 677 mW cm− 2 at 800 °C. The single cell operates stably for 250 h at a constant current of 0.3 A/cm2 without obvious degrading performance. According to all of the experimental results, the P02STC sample might be a promising candidate cathode for SOFCs.

Efficient perovskite cathode for solid oxide fuel cells towards enhanced oxygen reduction activity and stability by water-mediated exsolution

Highly efficient and stable cathodes are significantly vital for solid oxide fuel cells (SOFCs). However, one of key impediment to the cathode development is the undesirable oxygen reduction activity and stability with exposure upon steam. Herein, we present a novel nanoparticles-decorated cathode, comprised of O2−/e−/H+ triple-conducting K+-doped BaCo0.7Fe0.2Y0.1O3-δ (Ba0.9K0.1Co0.7Fe0.2Y0.1O3-δ, BKCFY) matrix oxide and the mixed O2−/e− conducting nanoparticles of BaCoO3-δ (BCO) through water-mediated exsolution process, exhibiting high activity and robust stability with exposure upon the steam. The cathode shows a low polarization resistance of 0.048 Ω cm2 at 700 °C when exposed upon humid air with 3% H2O, approximately 24% lower than that in dry air (0.065 Ω cm2 at 700 °C). Such improvement is mainly ascribed to the exsolved BaCoO3-δ nanoparticles decorated on the porous BKCFY, which enlarged the triple phase boundary for oxygen reduction reaction. The increased oxygen vacancy concentration through K doping can accelerate the Ba and Co ions segregation to form BaCoO3-δ with exposure upon the wet condition. Furthermore, K+ dopant with higher basicity than Ba2+ is beneficial for hydration behavior, which effectively promotes the catalytic activity under the water vapor. Moreover, the exsolved BaCoO3-δ nanoparticles are socketed on the BKCFY matrix oxide, which ensures high stability for this hybrid cathode operated at 700 °C. The findings provide a promising approach to design the triple-conducting cathode for solid oxide fuel cells via water-mediated exsolution, which can also be applied for solid oxide electrolysis cells and membrane reactors.

Enhancing Zn–CO2 battery with a facile Pd doped perovskite cathode for efficient CO2 to CO conversion

Using aqueous Zn–CO2 batteries to store renewable energy and produce valuable chemicals using CO2 as the source is a promising method for CO2 mitigation, that is alternative to traditional energy-costing CO2 capture/storage technologies. However, the lack of efficient CO2-reduction catalysts significantly hinders the efficiency of such batteries. In this study, an efficient perovskite cathode, Pd-doped La2CuO4, was successfully developed for the cathodic CO2 reduction reaction (CO2RR), and the optimal doping ratio of La2Cu1-xPdxO4 (x = 0.05) was determined. Compared with the pristine La2CuO4 catalyst, the current density for the CO2RR in the H-cell and the Faraday efficiency of CO production are both increased by ∼50% when operated −1.0 V (vs RHE). As a result, the peak power density of a Zn–CO2 battery using the Pd-doped La2CuO4 catalyst reached 0.75 mW cm−2 at 2.23 mA cm−2 by an enhancement ratio of 25%. Density functional theory calculations revealed that the *CO desorption processes on the cathode were enhanced owing to Pd doping, which accounted for the enhanced CO2RR activity and selectivity. The findings of this study show the potential application of perovskite catalysts in the cathode of Zn–CO2 batteries and provide an effective method for battery performance enhancement via the facile Pd doping.

Ti/Ni co-doped perovskite cathode with excellent catalytic activity and CO2 chemisorption ability via nanocatalysts exsolution for solid oxide electrolysis cell.

Carbon dioxide (CO2) gas is the main cause of global warming and has a significant effect on both climate change and human health. In this study, Ni/Ti co-doped Sr1.95Fe1.2Ni0.1Ti0.2Mo0.5O6-δ (SFNTM) double perovskite oxides were prepared and used as solid oxide electrolysis cell (SOEC) cathode materials for effective CO2 reduction. Ti-doping enhances the structural stability of the cathode material and increases the oxygen vacancy concentration. After treatment in 10% H2/Ar at 800°C, Ni nanoparticles were exsolved in situ on the SFNTM surface (Ni@SFNTM), thereby improving its chemisorption and activation capacity for CO2. Modified by the Ti-doping and the in situ exsolved Ni nanoparticles, the single cell with Ni@SFNMT cathode exhibits improved catalytic activity for CO2 reduction, exhibiting a current density of 2.54 A cm−2 at 1.8 V and 800°C. Furthermore, the single cell shows excellent stability after 100 h at 1.4 V, indicating that Ni/Ti co-doping is an effective strategy for designing novel cathode material with high electrochemical performance for SOEC.

(Invited) Effect of Atomic-Scale Surface Overcoat By Atomic Layer Deposition on Dopant Segregation of Perovskite Cathodes

Intense research has been performed to advance the solid oxide cell (SOC) technology because of their excellent efficiency for clean energy conversion and storage, but the lack of long-term durability, particularly of perovskite (ABO3)-based air electrodes, is currently the main technological bottleneck for wider commercial adoption. Long-term durability of SOC air electrodes has been mainly hampered by surface segregation of A-site dopant and morphological agglomeration. Since a deposition of an atomically thin oxide has proven to be highly effective in suppressing electrode agglomeration, a successful suppression of dopant segregation with the same approach will enhance the durability of air electrodes significantly by killing two birds with one stone. In the previous study [1], we demonstrated the effectiveness of an atomic scale overcoat in suppressing particle agglomeration. In this presentation, we demonstrate that even a few angstroms of metal oxide overcoat by atomic layer deposition (ALD) affects the behavior of Sr segregation in the underlying La0.8Sr0.2MnO3 (LSM) electrode significantly. By leveraging angle-resolved X-ray photoelectron spectroscopy (ARXPS), we provide a quantitative analysis of the relative atomic concentration on both the very surface and bulk of the electrode. Compared to bare LSM electrodes, those with 2 – 3 Å ALD overcoat show relatively high resistivity against Sr segregation when exposed to of 750 °C for 250 h. Particularly, an oxide overcoat with multi-valent cations (CeO2 and TiO2) tends to suppress Sr segregation effectively and even drive Sr species back into the bulk of LSM while an overcoat with single valent cations (ZrO2 and Y2O3) exhibits little effect on Sr segregation. It was further demonstrated that the segregation behavior is nicely aligned with the electrode performance; those coated with CeO2 and TiO2 showed better thermal stability in terms of polarization resistance. Based upon the time evolution of Sr content, cationic valence states, and oxygen defect concentration in the vicinity of surface, we conjecture that the amount of oxygen defects formed by the overcoat and the resulting chemical potential gradient at the interface between the overcoat underlying LSM surface plays a pivotal role in the Sr segregation behavior. The authors acknowledge the support from National Science Foundation (DMR 1753383) and NASA MIRO program (NNX15AQ01A).

A 98.2% energy efficiency Li-O2 battery using a LaNi-0.5Co0.5O3 perovskite cathode with extremely fast oxygen reduction and evolution kinetics

Rechargeable lithium-oxygen (Li-O2) batteries have been regarded as a promising energy storage device, but its practical use is impeded by its low energy efficiency. Herein, a bi-functional catalytic perovskite LaNi0.5Co0.5O3 (LNCO) is employed as the cathode of an efficient Li-O2 battery with a molten nitrate salt electrolyte at 160 °C. It displays a stable low charge–discharge overpotential 50 mV with a high energy efficiency (EE) 98.2 % at 0.1 mA cm−2 for over 100 cycles. The excellent performance is attributed to the extremely fast oxygen reduction and evolution kinetics on the surface of LNCO. The discharge product is Li2O with a porous and fluffy morphology which facilitates the transfer of oxygen and other intermediate species. It is noted that Li2O as a discharge product enables a theoretical specific energy density of 5200 Wh kg−1, which is superior to the Li2O2 as product giving 3500 Wh kg−1 for those ambient temperature Li-O2 batteries.

A/B-site co-doping enabled fast oxygen reduction reaction and promoted CO2 tolerance of perovskite cathode for solid oxide fuel cells

The significant challenges facing the development of the cathode for intermediate-temperature solid oxide fuel cells (IT-SOFCs) are the poor oxygen reduction reaction (ORR) activity as well as the CO2 poisoning issues. Herein, an La/Nb co-doped perovskite Ba0.9La0.1Co0.7Fe0.2Nb0.1O3-δ (BLCFN) has been developed as a promising cathode for IT-SOFCs. The polarization resistance of BLCFN cathode is 0.073 Ω cm2 at 700 °C air. This remarkable improved ORR activity can be attributed to the increased oxygen vacancies caused by the introduction of La3+ and Nb5+ ions. Furthermore, the collaboration introduction of La3+ and Nb5+ ions greatly reduce the alkalinity of the BLCFN electrode, bringing excellent CO2-tolerance for BLCFN cathode. No carbonate is yielded on the surface of the BLCFN cathode. The improvement on CO2-tolerance for these cathodes is largely attributed to the introduction of Nb5+ ions, which have higher acidity and more powerful M − O bond, and the introduction of La3+ can improve the ORR activity of the material on this basis. The co-doping of La/Nb elements furtherly stabilizes the lattice structure. Overall, the high ORR activity and CO2-tolerance of the cathode manifest a bright application prospect for BLCFN cathode in SOFCs and other membrane reactors.

BaCO3 Nanoparticles-Modified Composite Cathode with Improved Electrochemical Oxygen Reduction Kinetics for High-Performing Ceramic Fuel Cells

The effects of the electrochemical oxygen reduction reaction (ORR) on the surface of single-phase perovskite cathodes are well understood, but its potential for use in a complex system consisting of different material types is unexplored. Herein, we report how BaCO3 nanoparticles-modified La0.6Sr0.4Co0.2Fe0.8O3-δ-Gd0.2Ce0.8O2-δ (LSCF–GDC)-composite cathodes improved the electrochemical oxygen reduction kinetics for high-performing ceramic fuel cells. Both X-ray diffraction (XRD) and thermogravimetric analysis (TGA) studies reveal that BaCO3 is stable, and that it does not show any solid-state reaction with LSCF–GDC at SOFCs’ required operating temperature. The electrochemical conductivity relaxation (ECR) study reveals that during the infiltration of BaCO3 nanoparticles into LSCF–GDC, the surface exchange kinetics (Kchem) are enhanced up to a factor of 26.73. The maximum power density of the NiO-YSZ anode-support cell is increased from 1.08 to 1.48 W/cm2 via surface modification at 750 °C. The modified cathode also shows an ultralow polarization resistance (Rp) of 0.027 Ω.cm2, which is ~4.4 times lower than that of the bare cathode (~0.12 Ω.cm2) at 750 °C. Such enhancement can be attributed to the accelerated oxygen surface exchange process, possibly through promoting the dissociation of oxygen molecules via the infiltration of BaCO3 nanoparticles. The density functional theory (DFT) illustrates the interaction mechanism between oxygen molecules and the BaCO3 surface.