Repairing Noise-Contaminated Low-Frequency Vibrational Spectra with an Attention U-Net.

Low-frequency vibrational modes in infrared (IR) and Raman spectra, often termed molecular fingerprints, are sensitive probes of subtle structural changes and chemical interactions. However, their inherent weakness and susceptibility to environmental interference make them challenging to detect and analyze. To tackle this issue, we developed a deep learning denoising protocol based on an attention-enhanced U-net architecture. This model leverages the inherent correlations between high- and low-frequency vibrational modes within a molecule, effectively reconstructing low-frequency spectral features from their high-frequency counterparts. We demonstrate the effectiveness of this method by recovering low-frequency signals of trans-1,2-bis(4-pyridyl)ethylene (BPE) adsorbed on an Ag surface, a representative system for surface enhancement Raman spectroscopy (SERS). Notably, the trained model exhibits promising transferability to SERS spectra acquired under different surface and external field conditions. Furthermore, we applied this method to experimental IR and Raman spectra of BPE, achieving high-quality, low-frequency spectral recovery.

Accelerating the Discovery of Efficient High-Entropy Alloy Electrocatalysts: High-Throughput Experimentation and Data-Driven Strategies.

High-entropy alloys (HEAs) present both significant potential and challenges for developing efficient electrocatalysts due to their diverse combinations and compositions. Here, we propose a procedural approach that combines high-throughput experimentation with data-driven strategies to accelerate the discovery of efficient HEA electrocatalysts for the hydrogen evolution reaction (HER). This enables the rapid preparation of HEA arrays with various element combinations and composition ratios within a model system. The intrinsic activity of the HEA arrays is swiftly screened using scanning electrochemical cell microscopy (SECCM), providing precise composition-activity data sets for the HEA system. An ensemble machine learning (EML) model is then used to predict the activity database for the composition subspace of the system. Based on these database results, two groups of promising catalysts are recommended and validated through actual electrocatalytic evaluations. This procedural approach, which combines high-throughput experimentation with data-driven strategies, provides a new pathway to accelerate the discovery of efficient HEA electrocatalysts.

Efficient Electrocatalyst Nanoparticles from Upcycled Class II Capacitors.

To move away from fossil fuels, the electrochemical reaction plays a critical role in renewable energy sources and devices. The anodic oxygen evolution reaction (OER) is always coupled with these reactions in devices but suffers from large energy barriers. Thus, it is important for developing efficient OER catalysts with low overpotential. On the other hand, there are large amounts of metals in electronic waste (E-waste), especially various transition metals that are promising alternatives for catalyzing OER. Hence, this work, which focuses on upcycling Class II BaTiO3 Multilayer Ceramic Capacitors, of which two trillion were produced in 2011 alone. We achieved this by first using a green solvent extraction method that combined the ionic liquid Aliquat® 336 and hydrochloride acid to recover a mixed solution of Ni, Fe and Cu cations, and then using such a solution to synthesize high potential catalysts NiFe hydroxide and NiCu hydroxide for OER. NiFe-hydroxide has been demonstrated to have faster OER kinetics than the NiCu-hydroxide and commercial c-RuO2. In addition, it showed promising results after the chronopotentiometry tests that outperform c-RuO2.

In Situ Synthesis and Microfabrication of High Entropy Alloy and Oxide Compounds by Femtosecond Laser Direct Writing under Ambient Conditions.

Synthesis and coating of multi-metal oxides (MMOs) and alloys on conductive substrates are indispensable to electrochemical applications, yet demand multiple, resource-intensive, and time-consuming processes. Herein, an alternative approach to the synthesis and coating of alloys and MMOs by femtosecond laser direct writing (FsLDW) is reported. A solution-based precursor ink is deposited and dried on the substrate and illuminated by a femtosecond laser. During the illumination, dried precursor ink is transformed to MMO/alloys and is simultaneously bonded to the substrate. The formulation of the alloy and MMO precursor ink for laser processing is universally applicable to a large family of oxides and alloys. The process is conducted at room temperature and in an open atmosphere. To demonstrate, a large family of 57 MMOs and alloys are synthesized from a group of 13 elements. As a proof of concept, Ni0.24 Co0.23 Cu0.24 Fe0.15 Cr0.14 high entropy alloy synthesized on stainless-steel foil by FsLDW is used for the oxygen evolution reaction, which achieves a current density of 10 mA cm-2 at a significantly low overpotential of 213 mV. Further, FsLDW can also achieve microfabrication of alloys/MMO with feature sizes down to 20 µm.

Reversible Al Metal Anodes Enabled by Amorphization for Aqueous Aluminum Batteries.

Aqueous aluminum metal batteries (AMBs) are regarded as one of the most sustainable energy storage systems among post-lithium-ion candidates, which is attributable to their highest theoretical volumetric capacity, inherent safe operation, and low cost. Yet, the development of aqueous AMBs is plagued by the incapable aluminum plating in an aqueous solution and severe parasitic reactions, which results in the limited discharge voltage, thus making the development of aqueous AMBs unsuccessful so far. Here, we demonstrate that amorphization is an effective strategy to tackle these critical issues of a metallic Al anode by shifting the reduction potential for Al deposition. The amorphous aluminum (a-Al) interfacial layer is triggered by an in situ lithium-ion alloying/dealloying process on a metallic Al substrate with low strength. Unveiled by experimental and theoretical investigations, the amorphous structure greatly lowers the Al nucleation energy barrier, which forces the Al deposition competitive to the electron-stealing hydrogen evolution reaction (HER). Simultaneously, the inhibited HER mitigates the passivation, promoting interfacial ion transfer kinetics and enabling steady aluminum plating/stripping for 800 h in the symmetric cell. The resultant multiple full cells using Al@a-Al anodes deliver approximately a 0.6 V increase in the discharge voltage plateau compared to that of bare Al-based cells, which far outperform all reported aqueous AMBs. In both symmetric cells and full cells, the excellent electrochemical performances are achieved in a noncorrosive, low-cost, and fluorine-free Al2(SO4)3 electrolyte, which is ecofriendly and can be easily adapted for sustainable large-scale applications. This work brings an intriguing picture of the design of metallic anodes for reversible and high-voltage AMBs.

Confining High-Valence Iridium Single Sites onto Nickel Oxyhydroxide for Robust Oxygen Evolution.

Enhancing activity and stability of iridium- (Ir-) based oxygen evolution reaction (OER) catalysts is of great significance in practice. Here, we report a vacancy-rich nickel hydroxide stabilized Ir single-atom catalyst (Ir1-Ni(OH)2), which achieves long-term OER stability over 260 h and much higher mass activity than commercial IrO2 in alkaline media. In situ X-ray absorption spectroscopy analysis certifies the obvious structure reconstruction of catalyst in OER. As a result, an active structure in which high-valence and peripheral oxygen ligands-rich Ir sites are confined onto the nickel oxyhydroxide surface is formed. In addition, the precise introduction of atomized Ir not only surmounts the large-range dissolution and agglomeration of Ir but also suppresses the dissolution of substrate in OER. Theoretical calculations further account for the activation of Ir single atoms and the promotion of oxygen generation by high-valence Ir, and they reveal that the deprotonation process of adsorbed OH is rate-determining.

Synergic Reaction Kinetics over Adjacent Ruthenium Sites for Superb Hydrogen Generation in Alkaline Media.

Ruthenium (Ru)-based electrocatalysts as platinum (Pt) alternatives in catalyzing hydrogen evolution reaction (HER) are promising. However, achieving efficient reaction processes on Ru catalysts is still a challenge, especially in alkaline media. Here, the well-dispersed Ru nanoparticles with adjacent Ru single atoms on carbon substrate (Ru1,n -NC) is demonstrated to be a superb electrocatalyst for alkaline HER. The obtained Ru1,n -NC exhibits ultralow overpotential (14.8 mV) and high turnover frequency (1.25 H2  s-1 at -0.025 V vs reversible hydrogen electrode), much better than the commercial 40 wt.% Pt/C. The analyses reveal that Ru nanoparticles and single sites can promote each other to deliver electrons to the carbon substrate. Eventually, the electronic regulations bring accelerated water dissociation and reduced energy barriers of hydroxide/hydrogen desorption on adjacent Ru sites, then an optimized reaction kinetics for Ru1,n -NC is obtained to achieve superb hydrogen generation in alkaline media. This work provides a new insight into the catalyst design in simultaneous optimizations of the elementary steps to obtain ideal HER performance in alkaline media.

Efficient and Selective CO2 Reduction to Formate on Pd-Doped Pb3 (CO3 )2 (OH)2 : Dynamic Catalyst Reconstruction and Accelerated CO2 Protonation.

Exploring catalyst reconstruction under the electrochemical condition is critical to understanding the catalyst structure-activity relationship as well as to design effective electrocatalysts. Herein, a PbF2 nanocluster is synthesized and its self-reconstruction under the CO2 reduction condition is investigated. F- leaching, CO2 -saturated environment, and application of a cathodic potential induce self-reconstruction of PbF2 to Pb3 (CO3 )2 (OH)2 , which effectively catalyze the CO2 reduction to formate. The in situ formed Pb3 (CO3 )2 (OH)2 discloses >80% formate Faradaic efficiencies (FEs) across a broad range of potentials and achieves a maximum formate FE of ≈90.1% at -1.2 V versus reversible hydrogen electrode (RHE). Kinetic studies show that the CO2 reduction reaction (CO2 RR) on the Pb3 (CO3 )2 (OH)2 is rate-limited at the CO2 protonation step, in which proton is supplied by bicarbonate (HCO3 - ) in the electrolyte. To improve the CO2 RR kinetics, the Pb3 (CO3 )2 (OH)2 is further doped with Pd (4 wt%) to enhance its HCO3 - adsorption, which leads to accelerated protonation of CO2 . Therefore, the Pd-Pb3 (CO3 )2 (OH)2 (4 wt%) reveals higher formate FEs of >90% from -0.8 to -1.2 V versus RHE and reaches a maximum formate FE of 96.5% at -1.2 V versus RHE with a current density of ≈13 mA cm-2 .

Dynamic Restructuring of Cu-Doped SnS2 Nanoflowers for Highly Selective Electrochemical CO2 Reduction to Formate.

With ever-increasing energy consumption and continuous rise in atmospheric CO2 concentration, electrochemical reduction of CO2 into chemicals/fuels is becoming a promising yet challenging solution. Sn-based materials are identified as attractive electrocatalysts for the CO2 reduction reaction (CO2 RR) to formate but suffer from insufficient selectivity and activity, especially at large cathodic current densities. Herein, we demonstrate that Cu-doped SnS2 nanoflowers can undergo in situ dynamic restructuring to generate catalytically active S-doped Cu/Sn alloy for highly selective electrochemical CO2 RR to formate over a wide potential window. Theoretical thermodynamic analysis of reaction energetics indicates that the optimal electronic structure of the Sn active site can be regulated by both S-doping and Cu-alloying to favor formate formation, while the CO and H2 pathways will be suppressed. Our findings provide a rational strategy for electronic modulation of metal active site(s) for the design of active and selective electrocatalysts towards CO2 RR.

Anomalous self-optimization of sulfate ions for boosted oxygen evolution reaction.

Broadly, the oxygen evolution reaction (OER) has been deeply understood as a significant part of energy conversion and storage. Nevertheless, the anions in the OER catalysts have been neglected for various reasons such as inactive sites, dissolution, and oxidation, amongst others. Herein, we applied a model catalyst s-Ni(OH)2 to track the anionic behavior in the catalyst during the electrochemical process to fill this gap. The advanced operando synchrotron radiation Fourier transform infrared (SR-FTIR) spectroscopy, synchrotron radiation photoelectron spectroscopy (SRPES) depth detection and differential X-ray absorption fine structure (Δ-XAFS) spectrum jointly point out that some oxidized sulfur species (SO42-) will self-optimize new Ni-S bonds during OER process. Such amazing anionic self-optimization (ASO) behavior has never been observed in the OER process. Subsequently, the optimization-derived component shows a significantly improved electrocatalytic performance (activity, stability, etc.) compared to reference catalyst Ni(OH)2. Theoretical calculation further suggests that the ASO process indeed derives a thermodynamically stable structure of the OER catalyst, and then gives its superb catalytic performance by optimizing the thermodynamic and kinetic processes in the OER, respectively. This work demonstrates the vital role of anions in the electrochemical process, which will open up new perspectives for understanding OER and provide some new ideas in related fields (especially catalysis and chemistry).

Tuning the Electronic Structures of Multimetal Oxide Nanoplates to Realize Favorable Adsorption Energies of Oxygenated Intermediates.

Highly active oxygen evolution reaction (OER) electrocatalysts are important to effectively transform renewable electricity to fuel and chemicals. In this work, we construct a series of multimetal oxide nanoplate OER electrocatalysts through successive cation exchange followed by electrochemical oxidation, whose electronic structure and diversified metal active sites can be engineered via the mutual synergy among multiple metal species. Among the examined multimetal oxide nanoplates, CoCeNiFeZnCuOx nanoplates exhibit the optimal adsorption energy of OER intermediates. Together with the high electrochemical active surface area, the CoCeNiFeZnCuOx nanoplates manage to deliver a small overpotential of 211 mV at an OER current density of 10 mA cm-2 (η10) with a Tafel slope as low as 21 mV dec-1 in 1 M KOH solution, superior to commercial IrO2 (339 mV at η10, Tafel slope of 55 mV dec-1), which can be stably operated at 10 mA cm-2 (at an overpotential of 211 mV) and 100 mA cm-2 (at an overpotential of 307 mV) for 100 h.

An All-Organic D-A System for Visible-Light-Driven Overall Water Splitting.

Direct water splitting over photocatalysts is a prospective strategy to convert solar energy into hydrogen energy. Nevertheless, because of the undesirable electron accumulation at the surface, the overall water-splitting efficiency is seriously restricted by the poor charge separation/transfer ability. Here, an all-organic donor-acceptor (D-A) system through crafting carbon rings units-conjugated tubular graphitic carbon nitride (C-TCN) is proposed. Through a range of characterizations and theoretical calculations, the incorporation of carbon rings units via continuous π-conjugated bond builds a D-A system, which can drive intramolecular charge transfer to realize highly efficient charge separation. More importantly, the tubular structure and the incorporated carbon rings units cause a significant downshift of the valence band, of which the potential is beneficial to the activation for O2 evolution. When serving as photocatalyst for overall water splitting, C-TCN displays considerable performance with H2 and O2 production rates of 204.6 and 100.8 µmol g-1 h-1 , respectively. The corresponding external quantum efficiency reaches 2.6% at 405 nm, and still remains 1.7% at 420 nm. This work demonstrates that the all-organic D-A system conceptualized from organic solar cell can offer promotional effect for overall water splitting by addressing the charge accumulation problem rooted in the hydrogen evolution reaction.

A Unique Ru-N4-P Coordinated Structure Synergistically Waking Up the Nonmetal P Active Site for Hydrogen Production.

Numerous experiments have demonstrated that the metal atom is the active center of monoatomic catalysts for hydrogen evolution reaction (HER), while the active sites of nonmetal doped atoms are often neglected. By combining theoretical prediction and experimental verification, we designed a unique ternary Ru-N4-P coordination structure constructed by monodispersed Ru atoms supported on N,P dual-doped graphene for highly efficient hydrogen evolution in acid solution. The density functional theory calculations indicate that the charge polarization will lead to the most charge accumulation at P atoms, which results in a distinct nonmetallic P active sites with the moderate H∗ adsorption energy. Notably, these P atoms mainly supply highly efficient catalytic sites with ultrasmall absorption energy of 0.007 eV. Correspondingly, the Ru-N4-P demonstrated outstanding HER performance not only in an acidic condition but also in alkaline environment. Notably, the performance of Ru-NPC catalyst at high current is even superior to the commercial Pt/C catalysts, whether in acidic or alkaline medium. Our in situ synchrotron radiation infrared spectra demonstrate that a P-Hads intermediate is continually emerging on the Ru-NPC catalyst, actively proving the nonmetallic P catalytically active site in HER that is very different with previously reported metallic sites.

NiAg0.4 3D porous nanoclusters with epitaxial interfaces exhibiting Pt like activity towards hydrogen evolution in alkaline medium.

The necessity of Earth-abundant low-cost catalysts with activity similar to noble metals such as platinum is indispensable in order to realize the production of hydrogen through electrolysis of water. Herein, we report a relatively low-cost NiAg0.4 3D porous nanocluster catalyst whose activity matches with that of the state-of-the-art Pt/C in 1 M KOH solution. The catalyst is designed on the principle of creating an interface between a metal having a positive Gibbs energy of hydrogen adsorption and a metal of negative Gibbs energy based on the volcano plot, to tune the Gibbs energy of hydrogen adsorption near zero for enhanced hydrogen evolution. The synthesized NiAg0.4 3D porous nanoclusters are comprised of nanoparticles of lateral dimension ∼50 nm forming a 3D porous network with pores of 10 nm-80 nm. A high-resolution transmission electron microscopy image reveals the epitaxial growth of Ag (200) on the Ni (111) plane leading to the creation of abundant interfaces between the Ni and Ag lattices. The catalyst needs a low overpotential of 40 mV@10 mA cm-2 with a Tafel slope of 39.1 mV dec-1 in 1 M KOH solution. Furthermore, the catalyst exhibits a high specific activity of 0.1 mA cm-2(ECSA) at an overpotential (η) of 45 mV which matches with the specific activity of Pt/C 20% wt. catalyst (0.1 mA cm-2@η = 26 mV). Density functional theory calculations reveal that the Ni-Ag interface furnishes a pathway with a reduced Gibbs energy of adsorption of -0.04 eV, thus promoting enhanced hydrogen evolution. In summary, this study reveals excellent HER activity at the Ni-Ag interface.

Edge-Rich Fe-N4 Active Sites in Defective Carbon for Oxygen Reduction Catalysis.

Controllably constructing nitrogen-modified divacancies (ND) in carbon substrates to immobilize atomic Fe species and unveiling the advantageous configuration is still challenging, but indispensable for attaining optimal Fe-N-C catalysts for the oxygen reduction reaction (ORR). Herein, a fundamental investigation of unfolding intrinsically superior edge-ND trapped atomic Fe motifs (e-ND-Fe) relative to an intact center model (c-ND-Fe) in ORR electrocatalysis is reported. Density functional theory calculations reveal that local electronic redistribution and bandgap shrinkage for e-ND-Fe endow it with a lower free-energy barrier toward direct four-electron ORR. Inspired by this, a series of atomic Fe catalysts with adjustable ND-Fe coordination are synthesized, which verify that ORR performance highly depends on the concentration of e-ND-Fe species. Remarkably, the best e-ND-Fe catalyst delivers a favorable kinetic current density and halfwave potential that can be comparable to benchmark Pt-C under acidic conditions. This work will guide to develop highly active atomic metal catalysts through rational defect engineering.

Carbon Microtube Aerogel Derived from Kapok Fiber: An Efficient and Recyclable Sorbent for Oils and Organic Solvents.

A carbon microtube aerogel (CMA) with hydrophobicity, strong adsorption capacity, and superb recyclability was obtained by a feasible approach with economical raw material, such as kapok fiber. The CMA possesses a great adsorption capacity of 78-348 times its weight. Attributed to its outstanding thermal stability and excellent mechanical properties, the CMA can be used for many cycles of distillation, squeezing, and combustion without degradation, which suggests a potential practical application in oil-water separation. In addition, the adsorption capacity still retained 98% by distillation, 97% by squeezing, and 90% by combustion after 10 cycles. Therefore, the obtained CMA has a broad prospect as an economical, efficient, and environmentally friendly adsorbent.

Achieving Efficient Alkaline Hydrogen Evolution Reaction over a Ni5 P4 Catalyst Incorporating Single-Atomic Ru Sites.

Developing efficient electrocatalysts for alkaline water electrolysis is central to substantial progress of alkaline hydrogen production. Herein, a Ni5 P4 electrocatalyst incorporating single-atom Ru (Ni5 P4 -Ru) is synthesized through the filling of Ru3+ species into the metal vacancies of nickel hydroxides and subsequent phosphorization treatment. Electron paramagnetic resonance spectroscopy, X-ray-based measurements, and electron microscopy observations confirm the strong interaction between the nickel-vacancy defect and Ru cation, resulting in more than 3.83 wt% single-atom Ru incorporation in the obtained Ni5 P4 -Ru. The Ni5 P4 -Ru as an alkaline hydrogen evolution reaction catalyst achieves low onset potential of 17 mV and an overpotential of 54 mV at a current density of 10 mA cm-2 together with a small Tafel slope of 52.0 mV decade-1 and long-term stability. Further spectroscopy analyses combined with density functional theory calculations reveal that the doped Ru sites can cause localized structure polarization, which brings the low energy barrier for water dissociation on Ru site and the optimized hydrogen adsorption free energy on the interstitial site, well rationalizing the experimental reactivity.

Facile and eco-friendly preparation of super-amphiphilic porous polycaprolactone.

Super-amphiphilic (highly oleophilic and hydrophilic) materials have attracted tremendous interest for fundamental research and potential applications, owing to their unique affinity for both oil and water. In this work, a novel super-amphiphilic porous polycaprolactone (PCL) was fabricated via an efficient and eco-friendly method, in which stearic acid (SA) was used as both a porogen and a dopant precursor. The porous PCL had an interconnected hierarchical pore structure and was capable of absorbing oil and water rapidly. The complementary cooperation of the oleophilic and hydrophilic domains on the pore surface induced the amphiphilicity, while the capillary forces caused a wicking action. The synergy of the two effects gave rise to the super-wetting property. The special amphiphilic feature of the porous PCL had a positive effect on its biocompatibility and the material can be considered as a promising candidate for tissue engineering applications.

Electrochemical Conversion of CO2 to Syngas with Controllable CO/H2 Ratios over Co and Ni Single-Atom Catalysts.

The electrochemical CO2 reduction reaction (CO2 RR) to yield synthesis gas (syngas, CO and H2 ) has been considered as a promising method to realize the net reduction in CO2 emission. However, it is challenging to balance the CO2 RR activity and the CO/H2 ratio. To address this issue, nitrogen-doped carbon supported single-atom catalysts are designed as electrocatalysts to produce syngas from CO2 RR. While Co and Ni single-atom catalysts are selective in producing H2 and CO, respectively, electrocatalysts containing both Co and Ni show a high syngas evolution (total current >74 mA cm-2 ) with CO/H2 ratios (0.23-2.26) that are suitable for typical downstream thermochemical reactions. Density functional theory calculations provide insights into the key intermediates on Co and Ni single-atom configurations for the H2 and CO evolution. The results present a useful case on how non-precious transition metal species can maintain high CO2 RR activity with tunable CO/H2 ratios.

Amorphous Fe-Ni-P-B-O Nanocages as Efficient Electrocatalysts for Oxygen Evolution Reaction.

Electrocatalysts are one of the most important parts for oxygen evolution reaction (OER) to overcome the sluggish kinetics. Herein, amorphous Fe-Ni-P-B-O (FNPBO) nanocages as efficient OER catalysts are synthesized by a simple low-cost and scalable method at room temperature. The samples are chemically stable, in clear contrast to reported unstable or even pyrophoric boride samples. The Fe/Ni ratio of the FNPBO nanocages can be continuously adjusted to optimize the OER catalytic performance. The FNPBO nanocages composed of multicomponent elements can weaken the metal-metal bonds, thus rearranging the electron density around the catalytic metal atom centers and reducing the energy barrier for intermediate formation. Hence the optimized FNPBO (Fe6.4Ni16.1P12.9B4.3O60.2) catalyst shows superior intrinsic electrocatalytic activity for OER. The low overpotential to afford the current density of 10 mA cm-2 (236 mV), the small Tafel slope (39 mV dec-1), and the high specific current density (26.44 mA cm-2) at a given overpotential of 300 mV make a sharp contrast to state-of-the-art RuO2 (327 mV, 136 mV dec-1, and 0.028 mA cm-2, respectively).