ABSTRACT
The oxygen evolution reaction (OER) performance of ruthenium-based oxides strongly correlates with the electronic structures of Ru. However, the widely adopted monometal doping method unidirectionally regulates only the electronic structures, often failing to balance the activity and stability. Here, we propose an "elastic electron transfer" strategy to achieve bidirectional optimization of the electronic structures of Sr, Cr codoped RuO2 catalysts for acidic OER. The introduction of electron-withdrawing Sr intrinsically activates the Ru sites by increasing the oxidation state of Ru. Simultaneously, Cr acts as an electron buffer, donating electrons to Ru in the presence of Sr in the as-prepared catalysts and absorbing excess electrons from Sr leaching during the OER. Such a bidirectional regulation feature of Cr prevents overoxidation of Ru and maintains its high oxidation state during the OER. The optimal Ru3Cr1Sr0.175 catalyst exhibits a low overpotential (214 mV @ 10 mA cm-2) and excellent stability (over 300 h).
ABSTRACT
Defects can introduce atomic structural modulation and tailor performance of materials. Herein, it demonstrates that semiconductor WO3 with inert electrocatalytic behavior can be activated through defect-induced tensile strains. Structural characterizations reveal that when simply treated in Ar/H2 atmosphere, oxygen vacancies will generate in WO3 and cause defective structures. Stacking faults are found in defects, thus modulating electronic structure and transforming electrocatalytic-inert WO3 into highly active electrocatalysts. Density functional theory (DFT) calculations are performed to calculate *H adsorption energies on various WOx surfaces, revealing the oxygen vacancy composition and strain predicted to optimize the catalytic activity of hydrogen evolution reaction (HER). Such defective tungsten oxides can be integrated into commercial proton exchange membrane (PEM) electrolyser with comparable performance toward Pt-based PEM. This work demonstrates defective metal oxides as promising non-noble metal catalysts for commercial PEM green-hydrogen generation.
ABSTRACT
Developing an efficient photocatalytic system for hydrogen peroxide (H2O2) activation in Fenton-like processes holds significant promise for advancing water purification technologies. However, challenges such as high carrier recombination rates, limited active sites, and suboptimal H2O2 activation efficiency impede optimal performance. Here we show that single-iron-atom dispersed Bi2WO6 monolayers (SIAD-BWOM), designed through a facile hydrothermal approach, can offer abundant active sites for H2O2 activation. The SIAD-BWOM catalyst demonstrates superior photo-Fenton degradation capabilities, particularly for the persistent pesticide dinotefuran (DNF), showcasing its potential in addressing recalcitrant organic pollutants. We reveal that the incorporation of iron atoms in place of tungsten within the electron-rich [WO4]2- layers significantly facilitates electron transfer processes and boosts the Fe(II)/Fe(III) cycle efficiency. Complementary experimental investigations and theoretical analyses further elucidate how the atomically dispersed iron induces lattice strain in the Bi2WO6 monolayer, thereby modulating the d-band center of iron to improve H2O2 adsorption and activation. Our research provides a practical framework for developing advanced photo-Fenton catalysts, which can be used to treat emerging and refractory organic pollutants more effectively.
ABSTRACT
Urinary tract infections (UTIs), which can lead to pyelonephritis, urosepsis, and even death, are among the most prevalent infectious diseases worldwide, with a notable increase in treatment costs due to the emergence of drug-resistant pathogens. Current diagnostic strategies for UTIs, such as urine culture and flow cytometry, require time-consuming protocols and expensive equipment. We present here a machine learning-assisted colorimetric sensor array based on recognition of ligand-functionalized Fe single-atom nanozymes (SANs) for the identification of microorganisms at the order, genus, and species levels. Colorimetric sensor arrays are built from the SAN Fe1-NC functionalized with four types of recognition ligands, generating unique microbial identification fingerprints. By integrating the colorimetric sensor arrays with a trained computational classification model, the platform can identify more than 10 microorganisms in UTI urine samples within 1 h. Diagnostic accuracy of up to 97% was achieved in 60 UTI clinical samples, holding great potential for translation into clinical practice applications.
Subject(s)
Colorimetry , Machine Learning , Urinary Tract Infections , Urinary Tract Infections/diagnosis , Urinary Tract Infections/microbiology , Urinary Tract Infections/urine , Colorimetry/methods , Humans , Iron/chemistry , Biosensing Techniques/methodsABSTRACT
The present study attempts to explore the direct recyclability of glyceroborate from medicine pharmaceutical production wastewater into an aqueous lubricant instead of conventional waste processing methods from the tribological view. In order to determine the tribological feasibility, the physicochemical properties of crude pharmaceutical wastewater are investigated and compared with those of pure glycerol to access their potential lubrication properties. The results demonstrated that the crude pharmaceutical wastewater has better friction-reducing and antiwear properties under the same working conditions. Besides outstanding lubricating properties, the friction-induced formation of borate tribo-film and intermediate FeOOH compound favors lowering of the shear stress between the rubbing surfaces. This finding better provides an alternative to transform glyceroborate from medicine pharmaceutical production wastewater after simple distillation processing to a potential aqueous lubricant.
ABSTRACT
In this work, via engineering the conformation of cobalt active center in cobalt phthalocyanine molecular catalyst, the catalytic efficiency of electrochemical carbon monoxide reduction to methanol can be dramatically tuned. Based on a collection of experimental investigations and density functional theory calculations, it reveals that the electron rearrangement of the Co 3d orbitals of cobalt phthalocyanine from the low-spin state (S = 1/2) to the high-spin state (S = 3/2), induced by molecular conformation change, is responsible for the greatly enhanced CO reduction reaction performance. Operando attenuated total reflectance surface-enhanced infrared absorption spectroscopy measurements disclose accelerated hydrogenation of CORR intermediates, and kinetic isotope effect validates expedited proton-feeding rate over cobalt phthalocyanine with high-spin state. Further natural population analysis and density functional theory calculations demonstrate that the high spin Co2+ can enhance the electron backdonation via the dxz/dyz-2π* bond and weaken the C-O bonding in *CO, promoting hydrogenation of CORR intermediates.
ABSTRACT
Large-scale deployment of proton exchange membrane (PEM) water electrolyzers has to overcome a cost barrier resulting from the exclusive adoption of platinum group metal (PGM) catalysts. Ideally, carbon-supported platinum used at cathode should be replaced with PGM-free catalysts, but they often undergo insufficient activity and stability subjecting to corrosive acidic conditions. Inspired by marcasite existed under acidic environments in nature, we report a sulfur doping-driven structural transformation from pyrite-type cobalt diselenide to pure marcasite counterpart. The resultant catalyst drives hydrogen evolution reaction with low overpotential of 67 millivolts at 10 milliamperes per square centimeter and exhibits no degradation after 1000 hours of testing in acid. Moreover, a PEM electrolyzer with this catalyst as cathode runs stably over 410 hours at 1 ampere per square centimeter and 60°C. The marked properties arise from sulfur doping that not only triggers formation of acid-resistant marcasite structure but also tailors electronic states (e.g., work function) for improved hydrogen diffusion and electrocatalysis.
ABSTRACT
In the electrochemical CO2 reduction reaction (CO2RR), CO2 activation is always the first step, followed by the subsequent hydrogenation. The catalytic performance of CO2RR is intrinsically restricted by the competition between molecular CO2 activation and CO2 reduction product release. Here, we design a heteronuclear Fe1-Mo1 dual-metal catalytic pair on ordered porous carbon that features a high catalytic performance for driving electrochemical CO2 reduction to CO. Combining real-time near-ambient pressure X-ray photoelectron spectroscopy, operando 57Fe Mössbauer spectroscopy, and in situ attenuated total reflectance surface-enhanced infrared absorption spectroscopy measurements with density functional theory calculations, chemical adsorption of CO2 is observed on the Fe1-Mo1 catalytic pair through a bridge configuration, which prompts the bending of the CO2 molecule for CO2 activation and then facilitates the subsequent hydrogeneration reaction. More importantly, the dynamic adsorption configuration transition from the bridge configuration of CO2 on Fe1-Mo1 to the linear configuration of CO on the Fe1 center results in breaking the scaling relationship in CO2RR, simultaneously promoting the CO2 activation and the CO release.
ABSTRACT
Finding highly efficient hydrogen evolution reaction (HER) catalysts is pertinent to the ultimate goal of transformation into a net-zero carbon emission society. The design principles for such HER catalysts lie in the well-known structure-property relationship, which guides the synthesis procedure that creates catalyst with target properties such as catalytic activity. Here we report a general strategy to synthesize 10 kinds of single-atom-doped CoSe2-DETA (DETA = diethylenetriamine) nanobelts. By systematically analyzing these products, we demonstrate a volcano-shape correlation between HER activity and Co atomic configuration (ratio of Co-N bonds to Co-Se bonds). Specifically, Pb-CoSe2-DETA catalyst reaches current density of 10 mA cm-2 at 74 mV in acidic electrolyte (0.5 M H2SO4, pH ~0.35). This striking catalytic performance can be attributed to its optimized Co atomic configuration induced by single-atom doping.
ABSTRACT
Sub-1-nm structures are attractive for diverse applications owing to their unique properties compared to those of conventional nanomaterials. Transition-metal hydroxides are promising catalysts for oxygen evolution reaction (OER), yet there remains difficulty in directly fabricating these materials within the sub-1-nm regime, and the realization of their composition and phase tuning is even more challenging. Here we define a binary-soft-template-mediated colloidal synthesis of phase-selective Ni(OH)2 ultrathin nanosheets (UNSs) with 0.9 nm thickness induced by Mn incorporation. The synergistic interplay between binary components of the soft template is crucial to their formation. The unsaturated coordination environment and favorable electronic structures of these UNSs, together with in situ phase transition and active site evolution confined by the ultrathin framework, enable efficient and robust OER electrocatalysis. They exhibit a low overpotential of 309 mV at 100 mA cm-2 as well as remarkable long-term stability, representing one of the most high-performance noble-metal-free catalysts.
ABSTRACT
Layered Ni-rich cathodes, operating at high voltage with superior cyclic performance, are required to develop future high-energy Li-ion batteries. However, the worst lattice oxygen escape at the high-voltage region easily causes structural instability, rapid capacity fading and safety issues upon cycling. Here, we report a dual-track strategy to fully restrain the escape of lattice oxygen from Ni-rich cathodes within 2.7-4.5 V by one-step Ta doping and CeO2 coating according to their different diffusion energy barriers. The doped Ta can alleviate the charge compensation of oxygen anions as a positive charge centre to reduce the lattice oxygen escape and induce the formation of elongated primary particles, significantly inhibiting microcrack generation and propagation. Additionally, the layer of CeO2 coating effectively captures the remaining escaped oxygen and then the captured oxygen feeds back into the lattice during subsequent discharge. The resultant Ni-rich cathode enables a capacity of 231.3 mAh g-1 with a high initial coulombic efficiency of 93.5%. A pouch-type full cell comprising this cathode and a graphite anode exhibits >1000 times life cycles at 1C in the 2.7-4.5 V range, with 90.9% capacity retention.
ABSTRACT
High conversion efficiency over a wide operating potential window is important for the practical application of CO2 reduction electrocatalysis, yet that remains a huge challenge in differentiating the competing CO2 reduction and H2 evolution. Here we introduce point defects (Sn doping) and planar defects (grain boundary) into the Cu substrate. This multidimensional defect integration strategy guides the fabrication of highly diluted SnCu polycrystal, which exhibits high Faradaic efficiencies (>95%) toward CO2 electroreduction over an ultrawide potential window (ΔE = 1.3 V). The theoretical study indicates that the introduction of Sn doping and grain boundary synergistically provides an optimized electronic effect, which helps suppress H2 evolution and promotes the hydrogenation of *CO2.
ABSTRACT
Designing and synthesizing highly efficient and stable electrocatalysts for hydrogen evolution reaction (HER) is important for realizing the hydrogen economy. Tuning the electronic structure of the electrocatalysts is essential to achieve optimal HER activity, and interfacial engineering is an effective strategy to induce electron transfer in a heterostructure interface to optimize HER kinetics. In this study, ultrafine RhP2 /Rh nanoparticles are synthesized with a well-defined semiconductor-metal heterointerface embedded in N,P co-doped graphene (RhP2 /Rh@NPG) via a one-step pyrolysis. RhP2 /Rh@NPG exhibits outstanding HER performances under all pH conditions. Electrochemical characterization and first principles density functional theory calculations reveal that the RhP2 /Rh heterointerface induces electron transfer from metallic Rh to semiconductive RhP2 , which increases the electron density on the Rh atoms in RhP2 and weakens the hydrogen adsorption on RhP2 , thereby accelerating the HER kinetics. Moreover, the interfacial electron transfer activates the dual-site synergistic effect of Rh and P of RhP2 in neutral and alkaline environments, thereby promoting reorganization of interfacial water molecules for faster HER kinetics.
ABSTRACT
Precisely tailoring the electronic structures of electrocatalysts to achieve an optimum hydroxide binding energy (OHBE) is vital to the alkaline hydrogen oxidation reaction (HOR). As a promising alternative to the Pt-group metals, considerable efforts have been devoted to exploring highly efficient Ni-based catalysts for alkaline HOR. However, their performances still lack practical competitiveness. Herein, based on insights from the molecular orbital theory and the Hammer-Nørskov d-band model, we propose an ingenious surface oxygen insertion strategy to precisely tailor the electronic structures of Ni electrocatalysts, simultaneously increasing the degree of energy-level alignment between the adsorbed hydroxide (*OH) states and surface Ni d-band and decreasing the degree of anti-bonding filling, which leads to an optimal OHBE. Through the pyrolysis procedure mediated by a metal-organic framework at a low temperature under a reducing atmosphere, the obtained oxygen-inserted two atomic-layer Ni shell-modified Ni metal core nanoparticle (Ni@Oi-Ni) exhibits a remarkable alkaline HOR performance with a record mass activity of 85.63 mA mg-1, which is 40-fold higher than that of the freshly synthesized Ni catalyst. Combining CO stripping experiments with ab initio calculations, we further reveal a linear relationship between the OHBE and the content of inserted oxygen, which thus results in a volcano-type correlation between the OH binding strength and alkaline HOR activity. This work indicates that the oxygen insertion into the top-surface layers is an efficient strategy to regulate the coordination environment and electronic structure of Ni catalysts and identifies the dominate role of OH binding strength in alkaline HOR.
ABSTRACT
Phytoremediation is a potentially cost-effective and environmentally friendly remediation method for environmental pollution. However, the safe treatment and resource utilization of harvested biomass has become a limitation in practical applications. To address this, a novel manganese-carbon-based single-atom catalyst (SAC) method has been developed based on the pyrolysis of a manganese hyperaccumulator, Phytolacca americana. In this method, manganese atoms are dispersed atomically in the carbon matrix and coordinate with N atoms to form a Mn-N4 structure. The SAC developed exhibited a high photooxidation efficiency and excellent stability during the degradation of a common organic pollutant, rhodamine B. The Mn-N4 site was the active center in the transformation of photoelectrons via the transfer of photoelectrons between adsorbed O2 and Mn to produce reactive oxygen species, identified by in situ X-ray absorption fine structure spectroscopy and density functional theory calculations. This work demonstrates an approach that increases potential utilization of biomass during phytoremediation and provides a promising design strategy to synthesize cost-effective SACs for environmental applications.
Subject(s)
Environmental Restoration and Remediation , Phytolacca americana , Carbon/metabolism , Charcoal , Manganese/chemistry , Phytolacca americana/metabolismABSTRACT
Copper-based materials can reliably convert carbon dioxide into multi-carbon products but they suffer from poor activity and product selectivity. The atomic structure-activity relationship of electrocatalysts for the selectivity is controversial due to the lacking of systemic multiple dimensions for operando condition study. Herein, we synthesized high-performance CO2RR catalyst comprising of CuO clusters supported on N-doped carbon nanosheets, which exhibited high C2+ products Faradaic efficiency of 73% including decent ethanol selectivity of 51% with a partial current density of 14.4 mA/cm-2 at -1.1 V vs. RHE. We evidenced catalyst restructuring and tracked the variation of the active states under reaction conditions, presenting the atomic structure-activity relationship of this catalyst. Operando XAS, XANES simulations and Quasi-in-situ XPS analyses identified a reversible potential-dependent transformation from dispersed CuO clusters to Cu2-CuN3 clusters which are the optimal sites. This cluster can't exist without the applied potential. The N-doping dispersed the reduced Cun clusters uniformly and maintained excellent stability and high activity with adjusting the charge distribution between the Cu atoms and N-doped carbon interface. By combining Operando FTIR and DFT calculations, it was recognized that the Cu2-CuN3 clusters displayed charge-asymmetric sites which were intensified by CH3* adsorbing, beneficial to the formation of the high-efficiency asymmetric ethanol.
ABSTRACT
Unveiling the structural evolution and working mechanism of catalysts under realistic operating conditions is crucial for the design of efficient electrocatalysts for CO2 electroreduction, yet remains highly challenging. Here, by virtue of operando structural measurements at multiscale levels, it is identified under CO2 electroreduction conditions that an as-prepared CeO2/BiOCl precatalyst gradually evolves into CeOx/Bi interface structure with enriched Ce3+ species, which serves as the real catalytically active phase. The derived CeOx/Bi interface structure compared to pure Bi counterpart delivers substantially enhanced performance with a formate Faradaic efficiency approaching 90% for 24 hours in a wide potential window. The formate Faradaic efficiency can be further increased by using isotope D2O instead of H2O. Density functional theory calculations suggest that the regenerative CeOx/Bi interfacial sites can not only promote water activation to increase local *H species for CO2 protonation appropriately, but also stabilize the key intermediate *OCHO in formate pathway.
ABSTRACT
Electrosynthesis of hydrogen peroxide (H2 O2 ) in the acidic environment could largely prevent its decomposition to water, but efficient catalysts that constitute entirely earth-abundant elements are lacking. Here we report the experimental demonstration of narrowing the interlayer gap of metallic cobalt diselenide (CoSe2 ), which creates high-performance catalyst to selectively drive two-electron oxygen reduction toward H2 O2 in an acidic electrolyte. The enhancement of the interlayer coupling between CoSe2 atomic layers offers a favorable surface electronic structure that weakens the critical *OOH adsorption, promoting the energetics for H2 O2 production. Consequently, on the strongly coupled CoSe2 catalyst, we achieved Faradaic efficiency of 96.7 %, current density of 50.04â milliamperes per square centimeter, and product rate of 30.60â mg cm-2 h-1 . Moreover, this catalyst shows no sign of degradation when operating at -63 milliamperes per square centimeter over 100â hours.
ABSTRACT
While inheriting the exceptional merits of single atom catalysts, diatomic site catalysts (DASCs) utilize two adjacent atomic metal species for their complementary functionalities and synergistic actions. Herein, a DASC consisting of nickel-iron hetero-diatomic pairs anchored on nitrogen-doped graphene is synthesized. It exhibits extraordinary electrocatalytic activities and stability for both CO2 reduction reaction (CO2RR) and oxygen evolution reaction (OER). Furthermore, the rechargeable Zn-CO2 battery equipped with such bifunctional catalyst shows high Faradaic efficiency and outstanding rechargeability. The in-depth experimental and theoretical analyses reveal the orbital coupling between the catalytic iron center and the adjacent nickel atom, which leads to alteration in orbital energy level, unique electronic states, higher oxidation state of iron, and weakened binding strength to the reaction intermediates, thus boosted CO2RR and OER performance. This work provides critical insights to rational design, working mechanism, and application of hetero-DASCs.
ABSTRACT
π-d Conjugated coordination polymers (CCPs) have attracted much attention for various applications, although the chemical states and structures of many CCPs are still blurry. Now, a one-dimensional (1D) π-d conjugated coordination polymer for high performance sodium-ion batteries is presented. The chemical states of the obtained coordination polymer are clearly revealed. The electrochemical process undergoes a three-electron reaction and the structure transforms from C=N double bonds and NiII to C-N single bonds and NiI , respectively. Our unintentional experiments provided visual confirmation of NiI . The existence of NiI was further corroborated by its X-ray absorption near-edge structure (XANES) and its catalytic activity in Negishi cross-coupling.