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At least 1,243 records · Page 69

Contrasting responses of woody and grassland ecosystems to increased CO 2 as water supply varies

Experiments show that elevated atmospheric CO 2 (eCO 2 ) often enhances plant photosynthesis and productivity, yet this effect varies substantially and may be climate sensitive. Understanding if, where and how water supply regulates CO 2 enhancement is critical for projecting terrestrial responses to increasing atmospheric CO 2 and climate change. Here, using data from 14 long-term ecosystem-scale CO 2 experiments, we show that the eCO 2 enhancement of annual aboveground net primary productivity is sensitive to annual precipitation and that this sensitivity differs between woody and grassland ecosystems. During wetter years, CO 2 enhancement increases in woody ecosystems but declines in grass-dominated systems. Consistent with this difference, woody ecosystems can increase leaf area index in wetter years more effectively under eCO 2 than can grassland ecosystems. Overall, and across different precipitation regimes, woody systems had markedly stronger CO 2 enhancement (24%) than grasslands (13%). Finally, we developed an empirical relationship to quantify aboveground net primary productivity enhancement on the basis of changes in leaf area index, providing a new approach for evaluating eCO 2 impacts on the productivity of terrestrial ecosystems.

54 ENVIRONMENTAL SCIENCES↗

Gas diffusion electrodes, reactor designs and key metrics of low-temperature CO 2 electrolysers

We report that CO 2 emissions can be recycled via low-temperature CO 2 electrolysis to generate products such as carbon monoxide, ethanol, ethylene, acetic acid, formic acid and propanol. In recent years, progress has been made towards an industrially relevant performance by leveraging the development of gas diffusion electrodes (GDEs), which enhance the mass transport of reactant gases (for example, CO 2 ) to the active electrocatalyst. Innovations in GDE design have thus set new benchmarks for CO 2 conversion activity. In this Review, we discuss GDE-based CO 2 electrolysers, in terms of reactor designs, GDE composition and failure modes, to identify the key advances and remaining shortfalls of the technology. This is combined with an overview of the partial current densities, efficiencies and stabilities currently achieved and an outlook on how phenomena such as carbonate formation could influence the future direction of the field. Our aim is to capture insights that can accelerate the development of industrially relevant CO 2 electrolysers.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

Long-life lithium-ion batteries realized by low-Ni, Co-free cathode chemistry

The increasing demand for lithium-ion battery-powered electric vehicles (EVs) has led to a surge in recent prices of strategic battery materials such as cobalt (Co) and nickel (Ni). While all EV makers are eager to eliminate Co usage, Ni has rapidly become another ‘pain point’ for the industry, as its price is nearing half that of Co. The sustainability issue facing both Ni and Co puts forward a grand materials challenge, that is, to reduce Ni content and eliminate Co while maintaining high specific energy and stability. Here in this work, a complex concentrated doping strategy is used to eliminate Co in a commercial NMC-532 cathode. The LiNi 0.5 Mn 0.43 Ti 0.02 Mg 0.02 Nb 0.01 Mo 0.02 O 2 cathode shows potential cost advantage with relatively high specific energy and significantly improved overall performance (~95% capacity retained after 1,000 cycles in pouch-type cells, 2.8–4.3 V vs graphite, at 1 C, 1.5 mA cm -2 ). Combining X-ray techniques and electron microscopy, we uncover the origins of the superior stability.

36 MATERIALS SCIENCE↗

High-temperature high-pressure microfluidic system for rapid screening of supercritical CO 2 foaming agents

CO 2 foam helps to increase the viscosity of CO 2 flood fluid and thus improve the process efficiency of the anthropogenic greenhouse gas’s subsurface utilization and sequestration. Successful CO 2 foam formation mandates the development of high-performance chemicals at close to reservoir conditions, which in turn requires extensive laboratory tests and evaluations. This work demonstrates the utilization of a microfluidic reservoir analogue for rapid evaluation and screening of commercial surfactants (i.e., Cocamidopropyl Hydroxysultaine, Lauramidopropyl Betaine, Tallow Amine Ethoxylate, N,N,N' Trimethyl-N'-Tallow-1,3-diaminopropane, and Sodium Alpha Olefin Sulfonate) based on their performance to produce supercritical CO 2 foam at high salinity, temperature, and pressure conditions. The microfluidic analogue was designed to represent the pore sizes of the geologic reservoir rock and to operate at 100 °C and 13.8 MPa. Values of the pressure drop across the microfluidic analogue during flow of the CO 2 foam through its pore network was used to evaluate the strength of the generated foam and utilized only milliliters of liquid. The transparent microfluidic pore network allows in-situ quantitative visualization of CO 2 foam to calculate its half-life under static conditions while observing if there is any damage to the pore network due to precipitation and blockage. The microfluidic mobility reduction results agree with those of foam loop rheometer measurements, however, the microfluidic approach provided more accurate foam stability data to differentiate the foaming agent as compared with conventional balk testing. The results obtained here supports the utility of microfluidic systems for rapid screening of chemicals for carbon sequestration or enhanced oil recovery operations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

A red-light-powered silicon nanowire biophotochemical diode for simultaneous CO 2 reduction and glycerol valorization

A bias-free photochemical diode, in which a p-type photocathode is connected to an n-type photoanode to harness light for driving photoelectrochemical reduction and oxidation pairs, serves as a platform for realizing light-driven fuel generation from CO 2 . However, the conventional design, in which cathodic CO 2 reduction is coupled with the anodic oxygen evolution reaction (OER), requires substantial energy input. Here we present a photochemical diode device that harnesses red light (740 nm) to simultaneously drive biophotocathodic CO 2 -to-multicarbon conversion and photoanodic glycerol oxidation as an alternative to the OER to overcome the above thermodynamic limitation. The device consists of an efficient CO 2 -fixing microorganism, Sporomusa ovata, interfaced with a silicon nanowire photocathode and a Pt–Au-loaded silicon nanowire photoanode. This photochemical diode operates bias-free under low-intensity (20 mW cm –2 ) red light irradiation with ~80% Faradaic efficiency for both the cathodic and anodic products. Finally, this work provides an alternative photosynthetic route to mitigate excessive CO 2 emissions and efficiently generate value-added chemicals from CO 2 and glycerol.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Electrocatalytic CO 2 reduction on earth abundant 2D Mo 2 C and Ti 3 C 2 MXenes

Mo 2 C and Ti 3 C 2 MXenes were investigated as earth-abundant electrocatalyts for the CO 2 reduction reaction (CO 2 RR). Mo 2 C and Ti 3 C 2 exhibited faradaic efficiencies of 90% (250 mV overpotential) and 65% (650 mV overpotential), respectively, for the reduction of CO 2 to CO in acetonitrile using an ionic liquid electrolyte. The use of ionic liquid 1-ethyl-2-methylimidazolium tetrafluoroborate as an electrolyte in organic solvent suppressed the competing hydrogen evolution reaction. Density functional theory (DFT) calculations suggested that the catalytic active sites are oxygen vacancy sites on both MXene surfaces. Also, a spontaneous dissociation of adsorbed COOH species to a water molecule and adsorbed CO on Mo 2 C promote the CO 2 RR.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Molecular insight into the anion effect and free volume effect of CO 2 solubility in multivalent ionic liquids

For many years, experimental and theoretical studies have investigated the solubility of CO 2 in a variety of ionic liquids (ILs), but the overarching absorption mechanism is still unclear. Currently, two different factors are believed to dominate the absorption performance: (a) the fractional free volume (FFV) accessible for absorption; and (b) the nature of the CO 2 interactions with the anion species. The FFV is often more influential than the specific choice of the anion, but neither mechanism provides a complete picture. Herein, we have attempted to decouple these mechanisms in order to provide a more definitive molecular-level perspective of CO 2 absorption in IL solvents. We simulate a series of nine different multivalent ILs comprised of imidazolium cations and sulfonate/sulfonimide anions tethered to benzene rings, along with a comprehensive analysis of the CO 2 absorption and underlying molecular-level features. We find that the CO 2 solubility has a very strong, linear correlation with respect to FFV, but only when comparisons are constrained to a common anion species. The choice of anion results in a fundamental remapping of the correlation between CO 2 solubility and FFV. Overall, the free volume effect dominates in the ILs with smaller FFV values, while the choice of anion becomes more important in the systems with larger FFVs. Our proposed mechanistic map is intended to provide a more consistent framework for guiding further IL design for gas absorption applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Pt–Co truncated octahedral nanocrystals: a class of highly active and durable catalysts toward oxygen reduction

We report a facile and scalable synthesis of Pt–Co truncated octahedral nanocrystals (TONs) by employing Pt(acac) 2 and Co(acac) 2 as precursors, together with CO molecules and Mn atoms derived from the decomposition of Mn 2 (CO) 10 as a reductant and a {111} facet-directing agent, respectively. Both the composition and yield of the Pt–Co TONs could be varied through the introduction of CHCl 3 . When tested at 80 °C using membrane electrode assembly (MEA), the 4 nm Pt 2.6 Co TONs gave a mass activity of 294 A g Pt –1 at beginning-of-life (BOL) and it increased to 384 A g Pt –1 during recovery cycles. The mass activity at BOL only dropped by 24% after 30 000 voltage cycles at end-of-life (EOL) in a metal dissolution accelerated stress test. The Pt 2.6 Co/C catalyst outperformed the commercial TKK Pt 3 Co/C (230 A g Pt –1 at BOL and 40% loss after 30 000 cycles at EOL) in terms of both activity and durability. Our systematic analysis suggested that the enhancement in activity can be attributed to the combination of small, uniform size and well-defined {111} facets. This new class of catalysts holds promise for applications in proton-exchange membrane fuel cells.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Planar defect-driven electrocatalysis of CO 2 -to-C 2 H 4 conversion

The selectivity towards a specific C 2+ product, such as ethylene (C 2 H 4 ), is sensitive to the surface structure of copper (Cu) catalysts in carbon dioxide (CO 2 ) electro-reduction. The fundamental understanding of such sensitivity can guide the development of advanced electrocatalysts, although it remains challenging at the atomic level. In this work, we demonstrated that planar defects, such as stacking faults, could drive the electrocatalysis of CO 2 -to-C 2 H 4 conversion with higher selectivity and productivity than Cu(100) facets in the intermediate potential region (–0.50 ~ –0.65 V vs. RHE). The unique right bipyramidal Cu nanocrystals containing a combination of (100) facets and a set of parallel planar defects delivered 67% faradaic efficiency (FE) for C 2 H 4 and a partial current density of 217 mA cm –2 at –0.63 V vs. RHE. In contrast, Cu nanocubes with exclusive (100) facets exhibited only 46% FE for C 2 H 4 and a partial current density of 87 mA cm –2 at an identical potential. Both ex situ CO temperature-programmed desorption and in situ Raman spectroscopy analysis implied that the stronger *CO adsorption on planar defect sites facilitates CO generation kinetics, which contributes to a higher surface coverage of *CO and in turn an enhanced reaction rate of C–C coupling towards C 2+ products, especially C 2 H 4 .

36 MATERIALS SCIENCE↗

CO 2 methanation reaction pathways over unpromoted and NaNO 3 -promoted Ru/Al 2 O 3 catalysts

Catalytic CO 2 sorbents, materials that adsorb and pre-concentrate CO 2 on the catalyst surface prior to subsequent conversion, are becoming important materials in CO 2 capture and utilization. In this work, a prototypical CO 2 methanation catalyst – Ru/Al 2 O 3 – and a related catalytic sorbent – NaNO 3 /Ru/Al 2 O 3 – are used for CO 2 methanation in flowing hydrogen in a fixed bed reactor at temperatures ranging from 220 to 280 °C. Activation energies for the NaNO 3 /Ru/Al 2 O 3 material are slightly higher than unpromoted Ru/Al 2 O 3 catalysts, and the reaction orders vary more significantly. In situ IR spectroscopy and steady-state isotopic kinetic analysis (SSITKA) using in situ IR/MS spectroscopy show that bicarbonate and linear carbonyl species are the likely reaction intermediates over unpromoted Ru/Al 2 O 3 , while bidentate carbonate, formate and linear carbonyl species are among likely reaction intermediates over NaNO 3 /Ru/Al 2 O 3 . Rate laws consistent with the obtained experimental data are proposed after kinetic modeling of multiple plausible reaction pathways. In conclusion, results suggest that the pathway over the NaNO 3 /Ru/Al 2 O 3 catalyst likely has an additional kinetically relevant irreversible step in the CO 2 methanation reaction pathway.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Nanoconfinement matters in humidified CO 2 interaction with metal silicates

With enigmatic observations of enhanced reactivity of wet CO 2 -rich fluids with metal silicates, the mechanistic understanding of molecular processes governing carbonation proves critical in designing secure geological carbon sequestration and economical carbonated concrete technologies. Here, we use the first principle and classical molecular simulations to probe the impact of nanoconfinement on physicochemical processes at the rock–water–CO 2 interface. We choose nanoporous calcium–silicate–hydrate (C–S–H) and forsterite (Mg 2 SiO 4 ) as model metal silicate surfaces that are of significance in cement chemistry and geochemistry communities, respectively. We show that while a nanometer-thick interfacial water film persists at unsaturated conditions consistent with in situ infrared spectroscopy, the phase behavior of the water–CO 2 mixture changes from its bulk counterpart depending on the surface chemistry and nanoconfinement. We also observe enhanced solubility at the interface of water and CO 2 phases, which could amplify the CO 2 speciation rate. Additionally, through free energy calculations, we show that CO 2 could be found in a metastable state near the C–S–H surface, which can potentially react with surface water and hydroxyl groups to form carbonic acid and bicarbonate. These findings support the explicit consideration of nanoconfinement effects in reactive and non-reactive pore-scale processes.

54 ENVIRONMENTAL SCIENCES↗

Continuous-flow reactor with superior production rate and stability for CO 2 reduction using semiconductor photocatalysts

Semiconductor photocatalyst approaches for solar CO 2 reduction are attractive due to their simplicity but have lagged in efficiency compared to less-integrated photoelectrochemical (PEC) approaches and to electrolysis reactors. We identify poor mass transport and catalyst deactivation as key constraints. To address them, we have developed a continuous-flow photocatalytic reactor system allowing us to control the triple-phase interface on the photocatalyst surface using the liquid and reactant gas flow rates. With the goal of selectively producing CO, the reactor is optimized by controlling the pressure and flow rates of the reactant gas and electrolyte in contact with both sides with the intermediately placed catalyst. In comparison to batch reactors with an immobile photocatalyst bed and gas phase CO 2 or CO 2 purged water, 10–24 times higher production rates are achieved for photocatalysts such as TiO 2 , ZnO, C 3 N 4 , and CdS by simply changing to the designed flow-type photoreactor without any catalyst modification. In addition, CO selectivity (93.2%) and long-term stability (>780 min) using the designed reactor are significantly enhanced compared to using the batch reactors (71.7%, <180 min for reduced 50% activity). Here, we propose that the enhanced mass transport on the photocatalyst surface accelerates the desorption of the initial photolysis product, CO, and prevents the poisoning effect from deactivating photocatalyst activity. This study has the potential to facilitate the utilization of semiconductor-based photocatalytic reactions for achieving superior performance wih gaseous reactants.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Local microenvironment tuning induces switching between electrochemical CO 2 reduction pathways

Gas diffusion layers (GDL) have become a critical component in electrochemical CO 2 reduction (CO 2 R) systems because they can enable high current densities needed for industrially relevant productivity. Besides this function, it is often assumed that the choice of catalyst and electrolyte play much more important roles than the GDL in influencing the observed product selectivity. Here, we show that tuning of the GDL pore size can be used to control the local microenvironment of the catalyst and hence, effect significant changes in catalytic outcomes. This concept is demonstrated using sputtered Ag films on hydrophobic PTFE substrates with 6 different pore sizes. Although Ag is known to be a predominantly CO generating catalyst, we find that smaller pore sizes favor the generation of formate up to a faradaic efficiency of 43%. Combined experimental and simulation results show that this is due to the influence of the pore size on CO 2 mass transport, which alters the local pH at the electrode, resulting in reaction pathway switching between CO and formate. Importantly, our results highlight the importance of the local microenvironment as an experimental knob that can be rationally tuned for controlling product selectivity: a key consideration in the design of CO 2 R systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Deep learning of electrochemical CO 2 conversion literature reveals research trends and directions

Large-scale and openly available material science databases are mainly composed of computer simulation results rather than experimental data. Some examples include the Materials Project, Open Quantum Materials Database, and Open Catalyst 2022. Unfortunately, building large-scale experimental databases remains challenging due to the difficulties in consolidating locally distributed datasets. In this work, focusing on the catalysis literature of CO 2 reduction reactions (CO 2 RRs), we present a machine learning (ML)-based protocol for selecting highly relevant papers and extracting important experimental data. First, we report a document embedding method (Doc2Vec) for collecting papers of greatest relevance to the specific target domain, which yielded 3154 CO 2 RR-related papers from six publishers. Next, we developed named entity recognition (NER) models to extract twelve entities related to material names (catalyst, electrolyte, etc.) and catalytic performance (Faradaic efficiency, current density, etc.). Further, among several tested models, the MatBERT-based approach achieved the highest accuracy, with an average F1-score of 90.4% and an F1-score of 95.2% in a boundary relaxation evaluation scheme. The accurate and accelerated NER-based data extraction from a large volume of catalysis literature enables temporal trend analyses of the CO 2 RR catalysts, products, and performances, revealing the potentially effective material space in CO 2 RRs. While this work demonstrates the effectiveness of our ML-based text mining methods for specifically CO 2 RR literature, the methods and approach are applicable to and may be used to accelerate the development of other catalytic chemical reactions.

36 MATERIALS SCIENCE↗

Constructing a square-like copper cluster to boost C–C coupling for CO 2 electroreduction to ethylene

The CO 2 electroreduction reaction (CO 2 ER) to ethylene (C 2 H 4 ) offers the dual promise of lowering CO 2 emission while storing energy from renewable electricity, for which the development of highly efficient electrocatalysts is of great significance. Herein, by means of density functional theory (DFT) computations, we designed an electrocatalyst for CO 2 -to-C 2 H 4 conversion by anchoring a Cu 5 cluster supported on a MoS 2 monolayer with an S monovacancy (Cu 5 @MoS 2 ). Our results revealed that one Cu atom of the Cu 5 cluster was embedded into the framework of the defective MoS 2 monolayer, while the other four Cu atoms form a square-like island over the substrate surface. Interestingly, the C–C coupling between two *CO species can easily occur on the unique square-like active site with a low kinetic barrier of 0.56 eV to form the key *C 2 O 2 intermediate, which can then be hydrogenated to the C 2 H 4 product with a very low limiting potential (–0.32 eV). Significantly, alkaline conditions (pH = 13) are beneficial to further promote C 2 H 4 synthesis. Finally, our work may offer a new avenue to precisely modulate the structures of Cu clusters for converting CO 2 into high-value target products.

30 DIRECT ENERGY CONVERSION↗

Modeling diurnal and annual ethylene generation from solar-driven electrochemical CO 2 reduction devices

Integrated solar fuels devices for CO 2 reduction (CO 2 R) are a promising technology class towards reducing carbon emissions. Designing integrated CO 2 R solar fuels devices requires careful co-design of electrochemical and photovoltaic components as well as consideration of the diurnal and seasonal effects of solar irradiance, temperature, and other meteorological factors expected for ‘on-sun’ deployment. Using a photovoltaic-electrochemical (PV-EC) platform, we developed a temperature and potential-dependent diurnal and annual model using experimentally-determined CO 2 R performance of Cu-based electrocatalysts, local meteorological data from the National Solar Radiation Database (NSRD), and modeled performance of commercial c-Si PVs. Here we simulated gaseous diurnal product outputs with and without the effects of ambient temperature. From these outputs, we observed seasonal variation in gaseous product generation, with up to two-fold increases in ethylene productivity between the Winter and Summer, analyzed the consequences of dynamic cloud coverage, and identified periods where device cooling/heating mechanisms could be implemented to maximize ethylene generation. Finally, we modeled the annual ethylene generation for a scaled 1 MW solar farm at three different locations (Beijing, CN; Sydney, AUS; Barstow, CA) to determine the consequences of local meteorological climates on PV-EC CO 2 R product output, recording a maximum ethylene output of 18.5 tonne per year at Barstow. Overall, this model presents a critical tool for streamlining the translation of experimental solar-driven electrochemical research to real-world implementation.

14 SOLAR ENERGY↗

Percolative phase transition in few-layered MoSe 2 field-effect transistors using Co and Cr contacts

The metal-to-insulator phase transition (MIT) in two-dimensional (2D) materials under the influence of a gating electric field has revealed interesting electronic behavior and the need for a deeper fundamental understanding of electron transport processes, while attracting much interest in the development of next-generation electronic and optoelectronic devices. Although the mechanism of the MIT in 2D semiconductors is a topic under debate in condensed matter physics, our work demonstrates the tunable percolative phase transition in few-layered MoSe 2 field-effect transistors (FETs) using different metallic contact materials. Here, we attempted to understand the MIT through temperature-dependent electronic transport measurements by tuning the carrier density in a MoSe 2 channel under the influence of an applied gate voltage. In particular, we have examined this phenomenon using the conventional chromium (Cr) and ferromagnetic cobalt (Co) as two metal contacts. For both Cr and Co, our devices demonstrated n-type behavior with a room-temperature field-effect mobility of 16 cm 2 V −1 s −1 for the device with Cr-contacts and 92 cm 2 V −1 s −1 for the device with Co-contacts, respectively. Further, with low temperature measurements at 50 K, the mobilities increased significantly to 65 cm 2 V −1 s −1 for the device with Cr and 394 cm 2 V −1 s −1 for the device with Co-contacts. By fitting our experimental data to the percolative phase transition theory, the temperature-dependent conductivity data show a transition from an insulating-to-metallic behavior at a bias of ∼28 V for Cr-contacts and ∼20 V for Co-contacts. This cross-over of the conductivity can be attributed to an increase in carrier density as a function of the gate bias in temperature-dependent transfer characteristics. By extracting the critical exponents, we find that the transport behavior in the device with Co-contacts aligns closely with the 2D percolation theory. In contrast, the devices with Cr-contacts deviate significantly from the 2D limit at low temperatures.

36 MATERIALS SCIENCE↗

Ultra-stable and poison tolerant oxygen evolution activity enabled by surface In 2 O 3- x (OH) y of Co 3 In 2 S 2 large single crystals

Water is an earth-abundant source for clean hydrogen production via electrochemical water electrolysis (WE). However, the surface poisoning that occurs in aqueous electrolytes drastically deactivates the electrocatalytic performance of electrodes. Here, in this study, we report electrochemically formed In 2 O 3-x (OH) y on the surface of a large (1–1.5 mm long, 0.5–0.6 mm wide and 0.3–0.5 mm thick) single crystal of Weyl semimetal Co 3 In 2 S 2 (Co 3 In 2 S 2 /In 2 O 3-x (OH) y ) as an ultra-stable and poison tolerant electrode for the oxygen evolution reaction (OER) in 1 M KOH, addressing a bottleneck in WE. The OER activity of the powder form of Co 3 In 2 S 2 is limited by its aerophilic nature. Remarkably, the single-crystal electrodes maintained their high activity for a continuous operational period of 5 h in 1 M KOH electrolyte with/without 10 mM strong surface-poisoning ligands i.e., potassium cyanide, bipyridine, and ethylenediaminetetraacetate disodium salt. The electrodes exhibited stable OER activity for 1000 h at 100 mA cm -2 (1.73 V vs. RHE). The temperature-dependent OER polarization curves (10–70 °C) unambiguously revealed surface poisoning through the suppression of precatalytic Co-redox peaks on the bipyridine poisoned electrode, which led to the stabilization of surface Co-sites. The X-ray photoelectron spectroscopy analyses of pristine, poisoned and post-electrocatalytic single-crystal Co 3 In 2 S 2 electrodes revealed the existence of an In 2 O 3-x (OH) y surface phase, which could be the potential heterostructure for the origin of ultra-stable and poison tolerant OER activity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗