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At least 91 records · Page 5

Thermally Responsive Hydrogels for Passive Temperature Regulation under Direct Sunlight

By spontaneously emitting midinfrared radiation to outer space through the atmospheric window and reflecting sunlight, daytime radiative coolers achieve notable passive cooling performance. However, existing daytime radiative cooling systems generally lack the ability to adaptively switch between heating and cooling states based on ambient conditions. Herein a passive thermal regulation system that features a temperature‐dependent switchable solar reflectance from 0.05 (low temperature) to 0.8 (high temperature) is presented. This, along with a ≈0.95 midinfrared emittance, it enables automatic switching between radiative cooling and solar heating. Switchablity is enabled using a poly( N ‐isopropylacrylamide) (PNIPAM) hydrogel which exhibits high solar scattering above its tunable lower critical solution temperature (LCST) and transparency below its LCST. The lower part of the hydrogel is loaded with graphite to absorb solar energy in the heating state. In testing under sunny and partly cloudy outside conditions, this system maintains a temperature close to the set LCST.

Xie, Dajie↗

Proximity Ferroelectricity in Compositionally Graded Structures

Proximity ferroelectricity is a novel paradigm for inducing ferroelectricity in a non-ferroelectric polar material, such as AlN or ZnO that are typically unswitchable with an external field below their dielectric breakdown field. When placed in direct contact with a thin switchable ferroelectric layer (such as Al 1-x Sc x N or Zn 1-x Mg x O), they become a practically switchable ferroelectric. Using the thermodynamic Landau-Ginzburg-Devonshire theory, in this work, we perform the finite element modeling of the polarization switching in the compositionally graded AlN-Al 1-x Sc x N, ZnO-Zn 1-x Mg x O, and MgO-Zn 1-x Mg x O structures sandwiched in both a parallel-plate capacitor geometry as well as in a sharp probe-planar electrode geometry. We reveal that the compositionally graded structure allows the simultaneous switching of spontaneous polarization in the whole system by a coercive field significantly lower than the electric breakdown field of unswitchable polar materials. The physical mechanism is the depolarization electric field determined by the gradient of chemical composition “x”. The field lowers the steepness of the switching barrier in the otherwise unswitchable parts of the compositionally graded AlN-Al 1-x Sc x N and ZnO-Zn 1-x Mg x O structures. In the MgO-like regions of the compositionally graded MgO-Zn 1-x Mg x O structure, a shallow double-well free energy potential emerges. Proximity ferroelectric switching of the compositionally graded structures placed in the probe-electrode geometry occurs due to nanodomain formation under the tip. We predict that a gradient of chemical composition “x” significantly lowers effective coercive fields of the compositionally graded AlN-Al 1-x Sc x N and ZnO-Zn 1-x Mg x O structures compared to the coercive fields of the corresponding multilayers with a uniform chemical composition in each layer. A tip-induced switching further lowers the coercive field, enabling control of ferroelectric domains in otherwise unswitchable compositionally graded structures, which can provide nanoscale domain control for memory, actuation, sensing, and optical applications.

36 MATERIALS SCIENCE↗

Potential-induced wetting and dewetting in hydrophobic nanochannels for mass transport control

Wetting and dewetting transitions play a central role in controlling the hydrophobicity of the lining of biological channels in order to regulate aqueous solution permeation. Understanding of the operational characteristics of biological nanochannels led to experimental efforts to mimic their behavior and to achieve potential-induced, repeatedly-switchable wettability transitions in synthetic nanochannels in the early 2010s. Since then, research has identified conditions needed to produce reversible wettability transitions using a number of different environmental stimuli - such as light, pH, and electrostatic charge - in addition to potential. Furthermore, nascent understanding of the underlying phenomena in synthetic nanochannels was rapidly followed by practical applications, including oil-water separations, drug release, and electroactive flow control based on switchable wettability. Furthermore, more practical applications are being developed continuously, as the physical and chemical principles that govern hydrophobic gating at the nanoscale are further elucidated, making it possible to exploit wettability as a design element in nanofluidic systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Heteroepitaxial control of thickness, strain, and domain architecture in few-layer ferroelectric tin monochalcogenides

Thin-film epitaxy and epitaxial strain have been widely exploited to tune domain configurations, switching behavior, and ferroic properties in conventional three-dimensional ferroelectric thin films; however, its application to controlling the properties of two-dimensional (2D) ferroelectrics has remained largely unexplored. Here, using SnX (X = Se, S) as a model system, we demonstrate heteroepitaxial control of thickness, strain state, and domain architecture in few-layer ferroelectric SnX via growth on monolayer MoS2 van der Waals (vdW) templates. Compared with conventional growth, MoS2-templated heteroepitaxy promotes epitaxial alignment, yielding ultrathin SnSe films with improved crystalline quality, full areal coverage, and enlarged lateral dimensions. Strong interfacial epitaxial coupling induces pronounced in-plane strain and stabilizes a hierarchical ferroelastic domain architecture, in which long-range 90° stripe domains are further subdivided into nanoscale rotational variants, as revealed by scanning transmission electron microscopy and synchrotron X-ray microscopy. Piezoresponse force microscopy and second-harmonic polarimetry confirm robust in-plane polarization, while ferroelectricity in SnSe is established through polarization-electric field hysteresis and nonvolatile ferroelectric resistive switching with on/off ratios approaching 1000. A nonvolatile, switchable ferroelectric diode effect further evidences direct coupling between polarization and charge transport. Notably, ferroelectric switchability exhibits a strong thickness dependence and is preserved only below ∼10 layers. This vdW heteroepitaxial strategy is further extended to ferroelectric SnS. The seamless heteroepitaxial integration of 2D ferroelectrics with CMOS-compatible, wafer-scale MoS2 templates provides a general and scalable route for strain-enabled structural and ferroelectric engineering in emerging memory and low-power optoelectronic applications.

Wang, Yueyin↗

Electrochemical Switching of a Fluorescent Molecular Rotor Embedded within a Bistable Rotaxane

We report how the nanoconfined environment, introduced by the mechanical bonds within an electrochemically switchable bistable [2]rotaxane, controls the rotation of a fluorescent molecular rotor, namely, an 8-phenyl-substituted boron dipyrromethene (BODIPY). The electrochemical switching of the bistable [2]rotaxane induces changes in the ground-state coconformation and in the corresponding excited-state properties of the BODIPY rotor. In the starting redox state, when no external potential is applied, the cyclobis(paraquat-p-phenylene) (CBPQT4+) ring component encircles the tetrathiafulvalene (TTF) unit on the dumbbell component, leaving the BODIPY rotor unhindered and exhibiting low fluorescence. Upon oxidation of the TTF unit to a TTF2+ dication, the CBPQT4+ ring is forced toward the molecular rotor, leading to an increased energy barrier for the excited state to rotate the rotor into the state with a high nonradiative rate constant, resulting in an overall 3.4-fold fluorescence enhancement. On the other hand, when the solvent polarity is high enough to stabilize the excited charge-transfer state between the BODIPY rotor and the CBPQT4+ ring, movement of the ring toward the BODIPY rotor produces an unexpectedly strong fluorescence signal decrease as the result of photoinduced electron transfer from the BODIPY rotor to the CBPQT4+ ring. The nanoconfinement effect introduced by mechanical bonding can effectively lead to modulation of the physicochemical properties as observed in this bistable [2]rotaxane. On account of the straightforward synthetic strategy and the facile modulation of switchable electrochromic behavior, our approach could pave the way for the development of new stimuli-responsive materials based on mechanically interlocked molecules for future electro-optical applications, such as sensors, molecular memories, and molecular logic gates.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Correlating Mechanical Sensitivity with Spin Transition in the Explosive Spin Crossover Complex [Fe(Htrz) 3 ] n [ClO 4 ] 2 n

Spin crossover complexes are known to undergo bond length, volume, and enthalpy changes during spin transition. In an explosive spin crossover complex, these changes could affect the mechanical and initiation sensitivity of the explosive and lead to the development of a new class of sensitivity switchable materials. To explore this relationship, the well-known spin crossover compound [Fe(Htrz) 3 ] n [ClO 4 ] 2n (1) was re-evaluated for its explosive properties, and its mechanical impact sensitivity was correlated to spin transition. A variable temperature impact test was developed and used to evaluate the impact sensitivity of 1 in the low spin (LS, S = 0), thermally accessed high spin (HS, S = 2), and mixed LS and HS states. For comparison, the structurally similar Ni compound, [Ni(Htrz) 3 ] n [ClO 4 ] 2n (2), which does not undergo a spin transition at accessible temperatures, was synthesized and characterized, and its explosive properties and variable temperature impact sensitivity measured. These results reveal a correlation between impact sensitivity and spin transition, where 1 exhibits lower impact sensitivity in the LS state and increases in sensitivity upon transition to the HS state. Here, density functional theory was used to predict structural changes that occur upon spin transition that correlate to the change in sensitivity. This demonstrates, for the first time, an explosive spin crossover compound (ExSCO) that exhibits switchable impact sensitivity with a fully reversible internal switching mechanism.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Emergent properties at oxide interfaces controlled by ferroelectric polarization

Abstract Ferroelectric materials are characterized by the spontaneous polarization switchable by the applied fields, which can act as a “gate” to control various properties of ferroelectric/insulator interfaces. Here we review the recent studies on the modulation of oxide hetero-/homo-interfaces by ferroelectric polarization. We discuss the potential applications of recently developed four-dimensional scanning transmission electron microscopy and how it can provide insights into the fundamental understanding of ferroelectric polarization-induced phenomena and stimulate future computational studies. Finally, we give the outlook for the potentials, the challenges, and the opportunities for the contribution of materials computation to future progress in the area.

Chemistry↗

Candidate ferroelectrics via ab initio high-throughput screening of polar materials

Ferroelectrics are a class of polar and switchable functional materials with diverse applications, from microelectronics to energy conversion. Computational searches for new ferroelectric materials have been constrained by accurate prediction of the polarization and switchability with electric field, properties that, in principle, require a comparison with a nonpolar phase whose atomic-scale unit cell is continuously deformable from the polar ground state. For most polar materials, such a higher-symmetry nonpolar phase does not exist or is unknown. Here, we introduce a general high-throughput workflow that screens polar materials as potential ferroelectrics. We demonstrate our workflow on 1978 polar structures in the Materials Project database, for which we automatically generate a nonpolar reference structure using pseudosymmetries, and then compute the polarization difference and energy barrier between polar and nonpolar phases, comparing the predicted values to known ferroelectrics. Focusing on a subset of 182 potential ferroelectrics, we implement a systematic ranking strategy that prioritizes candidates with large polarization and small polar-nonpolar energy differences. To assess stability and synthesizability, we combine information including the computed formation energy above the convex hull, the Inorganic Crystal Structure Database id number, a previously reported machine learning-based synthesizability score, and ab initio phonon band structures. To distinguish between previously reported ferroelectrics, materials known for alternative applications, and lesser-known materials, we combine this ranking with a survey of the existing literature on these candidates through Google Scholar and Scopus databases, revealing ~130 promising materials uninvestigated as ferroelectric. Our workflow and large-scale high-throughput screening lays the groundwork for the discovery of novel ferroelectrics, revealing numerous candidates materials for future experimental and theoretical endeavors.

36 MATERIALS SCIENCE↗

Unconventional ferroelectricity in moiré heterostructures

Although all matter is composed of component particles, these particles can arrange themselves in various ways, giving rise to emergent phenomena that can be surprisingly rich and often cannot be understood by studying only the individual constituents. Discovering and understanding novel forms of emergence in quantum materials, especially in those where multiple degrees of freedom or energy scales are delicately balanced, is of great fundamental interest to condensed matter research. In this work, we report on the surprising observation of emergent ferroelectricity in graphene-based moiré heterostructures. Ferroelectric materials exhibit an electrically-switchable electric dipole, which is usually formed by spatial separation between the averaged centers of positive and negative charge within the unit cell. Based on this, it is difficult to imagine graphene, a material composed only of carbon atoms, exhibiting ferroelectricity. However, in this work, we indeed realize switchable ferroelectricity in Bernal-stacked bilayer graphene sandwiched between two hexagonal boron nitride (BN) layers. By introducing a moiré superlattice potential (via aligning bilayer graphene with the top and/or bottom BN crystals), we observe prominent and robust hysteretic behavior of the graphene resistance with an externally applied out-of-plane displacement field. Our systematic transport measurements reveal rich and striking response as a function of displacement field and electron filling, not previously observed in any 2D systems, and beyond the framework of conventional ferroelectrics. We further directly probe the ferroelectric polarization through a nonlocal monolayer graphene sensor. Our results suggest an unconventional, odd parity electronic ordering in the bilayer graphene/BN moiré system. This emergent moiré ferroelectricity may pave the way for ultrafast, programmable, and atomically thin carbon-based memory devices.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

Control over emergence and alignment of transient blisters in thermo-responsive gels using hierarchically patterned substrates

Surfaces with tunable microscale textures are vital in a large variety of technological applications, including heat transfer, antifouling and adhesion. To facilitate such broad-scale use, there is a need to create surfaces that undergo reconfigurable changes in topology and thus, enable switchable functionality. To date, there is a relative dearth of methods for engineering surfaces that can be actuated to change topography over a range of length scales, and hence, form tunable hierarchically structured layers. Combining modeling and experiments, we design a geometrically patterned, thermo-responsive poly (N-isopropylacrylamide) gel film that undergoes controllable hierarchical changes in topology with changes in temperature. At the bottom, the film is covalently bound to a solid, curved substrate; at the top, the film encompasses longitudinal rectangular ridges that are oriented perpendicular to the underlying cylindrical curves. At temperatures below lower critical solution temperature (LCST), the swollen gel exhibits 3D variations in polymer density and thickness defined by the gel's top and bottom topography. As the temperature rises above LCST, the interplay between the upper ridges and lower curves in the gel drives non-uniform, directional solvent transport, the nucleation and propagation of a phase-separated higher-density skin layer, and the resulting pressure buildup within the film. These different, interacting kinetic processes lead to an instability, which produces transient microscopic blisters in the film. Through simulations, we show how tuning the width of the ridges modifies the propagation of a skin layer and creates localized pressure build-up points, which enables control over the emergence, distribution, and alignment of the microscopic blisters. Futhermore, we provide a simple argument to predict the size of such microscopic features. Experiments confirm our predictions and further highlight how our computational model enables the rational design of topographical transitions in these tunable films. The development of actuatable, hierarchically structured films provides new routes for achieving switchable functionality in actuators, drug release systems and adhesives.

42 ENGINEERING↗

Ultrafast infrared plasmon switching in aligned carbon-nanotube optical resonators

Reconfigurable plasmonic materials are crucial components in active photonic devices for optical communication, signal processing, and sensing applications. Certain candidates including transparent conducting oxides, small-bandgap semiconductors (i.e. Ge, InSb), and conducting polymers can exhibit switchable free carrier concentrations triggered by optical, electrical or thermal excitations. Here, we show that aligned films of single-walled carbon nanotubes (SWCNTs) can serve as all-optically tunable plasmonic material in the mid-infrared range, thereby adding them to the library of switchable plasmonic materials. Interband optical pumping with femtosecond laser pulses results in the photoexcitation of free charge carriers, which transiently blueshifts the plasmon resonances of patterned, periodic SWCNT nano-resonators spanning the mid-infrared spectral range from 1700 to 2700 cm -1 . Furthermore. the ultrafast plasmon modulation exhibits a nearly single-picosecond decay time, attributed to interband carrier relaxation and inter-tube charge transfer. Given that aligned films of SWCNTs have high thermal stability, excellent photostability, epsilon-near-zero property, and extremely large optical anisotropy, their dynamic tunability represents a promising pathway towards active optical devices in the technologically important mid-infrared range.

single-walled carbon nanotubes↗

Ballistic Frenkel-exciton gate with a high on-off ratio

Here it is shown that the exciton interactions within organic dye aggregates, as modeled by the Frenkel Hamiltonian, enable the construction of an on/off switchable exciton gate. In this construction, a single exciton residing on a controlling gate molecule may pass or inhibit the ballistic propagation of an exciton in a proximal gate channel consisting of an array of dye molecules. High on-off ratios in excess of 102 can be achieved through the use of static difference dipole-dipole interactions between the gate and the gate channel which effectively creates a switchable Bragg grating. The gate channel and controlling gate molecule exhibit entanglement with the quantum mechanical superposition of the presence and absence of exciton occupation on the gate molecule.

74 ATOMIC AND MOLECULAR PHYSICS↗

Thermodynamic Theory of Proximity Ferroelectricity

Proximity ferroelectricity has recently been reported as a new design paradigm for inducing ferroelectricity, where a nonferroelectric polar material becomes a ferroelectric one by interfacing with a thin ferroelectric layer. Strongly polar materials, such as AlN and ZnO, which were previously unswitchable with an external field below their dielectric breakdown fields, can now be switched with practical coercive fields when they are in intimate proximity to a switchable ferroelectric. Here, we develop a general Landau-Ginzburg theory of proximity ferroelectricity in multilayers of nonferroelectrics and ferroelectrics to analyze their switchability and coercive fields. The theory predicts regimes of both “proximity switching,” where the multilayers collectively switch, and “proximity suppression,” where they collectively do not switch. The mechanism of the proximity ferroelectricity is an internal electric field determined by the polarization of the layers and their relative thickness in a self-consistent manner that renormalizes the double-well ferroelectric potential to lower the steepness of the switching barrier. Further reduction in the coercive field emerges from charged defects in the bulk that act as nucleation centers. The application of the theory to proximity ferroelectricity in Al x−1⁢ Sc x ⁢N/AlN and Zn 1−x ⁢Mg x ⁢O/ZnO bilayers is demonstrated. The theory further predicts that dielectric-ferroelectric and paraelectric-ferroelectric multilayers can potentially lead to induced ferroelectricity in the dielectric or paraelectric layers, resulting in the entire stack being switched, an exciting avenue for new discoveries. This thawing of “frozen ferroelectrics,” paraelectrics, and potentially dielectrics with high dielectric constants promises a large class of new ferroelectrics with exciting prospects for previously unrealizable domain-patterned optoelectronic and memory technologies.

36 MATERIALS SCIENCE↗

Tip-based proximity ferroelectric switching and piezoelectric response in wurtzite multilayers

Proximity ferroelectricity is a paradigm for inducing ferroelectricity when a nonferroelectric polar material (such as Al⁢ N), which is unswitchable with an external field below the dielectric breakdown field, becomes a practically switchable ferroelectric in direct contact with a thin switchable ferroelectric layer (such as Al 1−𝑥 ⁢Sc 𝑥 ⁢N). Here, we develop a Landau-Ginzburg-Devonshire approach to study the proximity effect of local piezoelectric response and polarization reversal in wurtzite ferroelectric multilayers under a sharp electrically biased tip. Using finite-element modeling, we analyze the probe-induced nucleation of nanodomains, the features of local polarization hysteresis loops and coercive fields in the Al 1−𝑥 ⁢Sc 𝑥 ⁢N/Al⁢ N bilayers and three-layers. Similar to the wurtzite multilayers sandwiched between two parallel electrodes, the regimes of “proximity switching” (when all layers collectively switch) and the regime of “proximity suppression” (when they collectively do not switch) are the only two possible regimes in the probe-electrode geometry. However, the parameters and asymmetry of the local piezoresponse and polarization hysteresis loops depend significantly on the sequence of the layers with respect to the probe. The physical mechanism of proximity ferroelectricity in the local probe geometry is a depolarizing electric field determined by the polarization of the layers and their relative thickness. The field, whose direction is opposite to the polarization vector in the layer(s) with the larger spontaneous polarization (such as Al⁢ N), renormalizes the double-well ferroelectric potential to lower the steepness of the switching barrier in the “otherwise unswitchable” polar layers. Tip-based control of domains in otherwise nonferroelectric layers using proximity ferroelectricity can provide nanoscale control of domain reversal in memory, actuation, sensing, and optical applications. The ability of the tip-induced proximity switching to differentially switch multilayers, based on the order of the layers, provides a powerful tool for selective domain engineering.

36 MATERIALS SCIENCE↗

Colloquium : Physical properties of group-IV monochalcogenide monolayers

The state-of-the-art knowledge of ferroelectric and ferroelastic group-IV monochalcogenide monolayers is surveyed. These semiconductors feature remarkable structural and mechanical properties, such as a switchable in-plane spontaneous polarization, soft elastic constants, structural degeneracies, and thermally driven two-dimensional structural transformations. Additionally, these 2D materials display selective valley excitations, valley Hall effects, and persistent spin helix behavior. After a description of their Raman spectra, a discussion of optical properties arising from their lack of centrosymmetry (such as an unusually strong second-harmonic intensity, large bulk photovoltaic effects, photostriction, and tunable exciton binding energies) is provided as well. Here, the physical properties observed in these materials originate from (correlate with) their intrinsic and switchable electric polarization, and the physical behavior hereby reviewed could be of use in nonvolatile memory, valleytronic, spintronic, and optoelectronic devices: these 2D multiferroics enrich and diversify the 2D material toolbox.

2D ferroelectrics↗

Frequency and time multiplexing for multiphoton state generation

One of the primary challenges with photonic quantum information processing is that single-photon states are created and heralded probabilistically, rather than being created on demand. One solution to this problem is multiplexing , which is attempting probabilistic generation of a single photon at multiple locations, times, or frequencies, and switching one successfully generated photon into an output mode. Motivated by the development of frequency-based photonic quantum information processing, we consider multiplexing using frequency and time as our options to use to get many photon generation opportunities. We devise an approach for generating multiphoton states, with photons populating multiple frequency modes in the same spatiotemporal mode. This method uses a variable-length optical delays to manipulate the temporal mode of the photons, and spaced fiber Bragg grating (FBG) reflectors to jointly manipulate the frequency and temporal modes of the photons. Experimental progress toward implementing this multiplexing scheme is proceeding along 2 fronts, each with different ways to achieve the variable-length optical delay. First, we will implement this scheme using a free-space optical quantum memory with multiple discretely adjustable free-space delays. For this implementation method, I calculate multiphoton generation rates, accounting for loss, that are realistically achievable with commercially available hardware. This work will appear in a theory paper, currently in preparation. Second, we will implement this multiplexing scheme in an integrated manner: the variable-length optical delay will happen on-chip using a long-lifetime Q-switchable Fabry-Perot cavity. The joint manipulation of the frequency and temporal modes of the photons will still happen off-chip in fiber with FBG reflectors. I report on experimental progress in constructing integrated Q-switchable Fabry-Perot cavities.

97 MATHEMATICS AND COMPUTING↗

Energy and Comfort Impacts of High Performance Facades in Office Buildings

Building facades have a major effect on energy use, occupant comfort, and well-being. Yet adoption of high-performance facades is often slowed by limited data and unclear cost benefits. To address this gap, Oak Ridge National Laboratory, in collaboration with the Facade Tectonics Institute, conducted whole-building energy simulations to evaluate fenestration technologies for small and medium office buildings across three weather locations: hot (Tampa, Florida, weather zone 2A), mixed (New York, New York, weather zone 4A), and cold (Rochester, Minnesota, weather zone 6A). The simulations included parametric variations in window-to-wall ratio (30%–70%), U-values (0.1–1 Btu/h∙ft 2 ∙°F), solar heat gain coefficients (0.2–0.8), and solar control strategies and devices (e.g., interior shades and switchable glazing). Performance metrics included annual cooling, heating, and total heating, ventilation and air-conditioning (HVAC) energy use intensity, as well as nonenergy factors such as useful daylight illuminance, glare frequency, and thermal comfort during typical office hours (8 a.m.–6 p.m.). Results indicate that cooling energy consumption is most sensitive to solar heat gain coefficient (SHGC) in hot weather, whereas heating energy consumption is strongly influenced by U-value in cold weather. Total HVAC reflects these trade-offs, showing up to 60% difference for a window in total HVAC energy use intensity between different combinations of U-value and SHGC. Daylight dimming generally reduces cooling loads but can increase heating demands in colder locations. Interior solar shades improve useful daylight and reduce discomfort glare, whereas switchable glazing delivers the largest cooling reductions in hot weather but may increase heating loads in winter by limiting passive solar gains. Thermal comfort improves with lower window-to-wall ratios and lower SHGC in hot locations and with lower U-values in cold locations.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

Switching CO 2 Electroreduction Selectivity Between C 1 and C 2 Hydrocarbons on Cu Gas-Diffusion Electrodes

We report that regulating the selectivity toward a target hydrocarbon product is still the focus of CO 2 electroreduction. Here, we discover that the original surface Cu species in Cu gas-diffusion electrodes plays a more important role than the surface roughness, local pH, and facet in governing the selectivity toward C 1 or C 2 hydrocarbons. The selectivity toward C 2 H 4 progressively increases, while CH 4 decreases steadily upon lowering the Cu oxidation species fraction. At a relatively low electrodeposition voltage of 1.5 V, the Cu gas-diffusion electrode with the highest Cu δ+ /Cu 0 ratio favors the pathways of hydrogenation to form CH 4 with maximum Faradaic efficiency of 65.4% and partial current density of 228 mA cm -2 at -0.83 V vs RHE. At 2.0 V, the Cu gas-diffusion electrode with the lowest Cu δ+ /Cu 0 ratio prefers C–C coupling to form C 2+ products with Faradaic efficiency topping 80.1% at -0.75 V vs RHE, where the Faradaic efficiency of C 2 H 4 accounts for 46.4% and the partial current density of C 2 H 4 achieves 279 mA cm -2 . This work demonstrates that the selectivity from CH 4 to C 2 H 4 is switchable by tuning surface Cu species composition of Cu gas-diffusion electrodes.

36 MATERIALS SCIENCE↗