Electron Accumulation Induced by Electron Injection-Incomplete Discharge on NiFe LDH for Enhanced Oxygen Evolution Reaction.

Optimizing the local electronic structure of electrocatalysts can effectively lower the energy barrier of electrochemical reactions, thus enhancing the electrocatalytic activity. However, the intrinsic contribution of the electronic effect is still experimentally unclear. In this work, the electron injection-incomplete discharge approach to achieve the electron accumulation (EA) degree on the nickel-iron layered double hydroxide (NiFe LDH) is proposed, to reveal the intrinsic contribution of EA toward oxygen evolution reaction (OER). Such NiFe LDH with EA effect results in only 262 mV overpotential to reach 50 mA cm-2, which is 51 mV-lower compared with pristine NiFe LDH (313 mV), and reduced Tafel slope of 54.8 mV dec-1 than NiFe LDH (107.5 mV dec-1). Spectroscopy characterizations combined with theoretical calculations confirm that the EA near concomitant Vo can induce a narrower energy gap and lower thermodynamic barrier to enhance OER performance. This study clarifies the mechanism of the EA effect on OER activity, providing a direct electronic structure modulation guideline for effective electrocatalyst design.

Strengthening the Synergy between Oxygen Vacancies in Electrocatalysts for Efficient Glycerol Electrooxidation.

Defect-engineered bimetallic oxides exhibit high potential for the electrolysis of small organic molecules. However, the ambiguity in the relationship between the defect density and electrocatalytic performance makes it challenging to control the final products of multi-step multi-electron reactions in such electrocatalytic systems. In this study, controllable kinetics reduction is used to maximize the oxygen vacancy density of a Cu─Co oxide nanosheet (CuCo2O4 NS), which is used to catalyze the glycerol electrooxidation reaction (GOR). The CuCo2O4-x NS with the highest oxygen-vacancy density (CuCo2O4-x-2) oxidizes C3 molecules to C1 molecules with selectivity of almost 100% and a Faradaic efficiency of ≈99%, showing the best oxidation performance among all the modified catalysts. Systems with multiple oxygen vacancies in close proximity to each other synergistically facilitate the cleavage of C─C bonds. Density functional theory calculations confirm the ability of closely spaced oxygen vacancies to facilitate charge transfer between the catalyst and several key glycolic-acid (GCA) intermediates of the GOR process, thereby facilitating the decomposition of C2 intermediates to C1 molecules. This study reveals qualitatively in tuning the density of oxygen vacancies for altering the reaction pathway of GOR by the synergistic effects of spatial proximity of high-density oxygen vacancies.

Strongly-Interacted NiSe2/NiFe2O4 Architectures Built Through Selective Atomic Migration as Catalysts for the Oxygen Evolution Reaction.

The interactions between the catalyst and support are widely used in many important catalytic reactions but the construction of strong interaction with definite microenvironments to understand the structure-activity relationship is still challenging. Here, strongly-interacted composites are prepared via selective exsolution of active NiSe2 from the host matrix of NiFe2O4 (S-NiSe2/NiFe2O4) taking advantage of the differences of migration energy, in which the NiSe2 possessed both high dispersion and small size. The characteristics of spatially resolved scanning transmission X-ray microscopy (STXM) coupled with analytical Mössbauer spectra for the surface and bulk electronic structures unveiled that this strongly interacted composite triggered more charge transfers from the NiSe2 to the host of NiFe2O4 while stabilizing the inherent atomic coordination of NiFe2O4. The obtained S-NiSe2/NiFe2O4 exhibits overpotentials of 290 mV at 10 mA cm-2 for oxygen evolution reaction (OER). This strategy is general and can be extended to other supported catalysts, providing a powerful tool for modulating the catalytic performance of strongly-interacted composites.

Electrocatalysis of nitrogen pollution: transforming nitrogen waste into high-value chemicals.

On 16 June 2023, the United Nations Environment Programme highlighted the severity of nitrogen pollution faced by humans and called for joint action for sustainable nitrogen use. Excess nitrogenous waste (NW: NO, NO2, NO2-, NO3-, etc.) mainly arises from the use of synthetic fertilisers, wastewater discharge, and fossil fuel combustion. Although the amount of NW produced can be minimised by reducing the use of nitrogen fertilisers and fossil fuels, the necessity to feed seven billion people on Earth limits the utility of this approach. Compared to current industrial processes, electrocatalytic NW reduction or CO2-NW co-reduction offers a potentially greener alternative for recycling NW and producing high-value chemicals. However, upgrading this technology to connect upstream and downstream industrial chains is challenging. This viewpoint focuses on electrocatalytic NW reduction, a cutting-edge technology, and highlights the challenges in its practical application. It also discusses future directions to meet the requirements of upstream and downstream industries by optimising production processes, including the pretreatment and supply of nitrogenous raw materials (e.g. flue gas and sewage), design and macroscopic preparation of electrocatalysts, and upscaling of reactors and other auxiliary equipment.

One-dimensional carbon based nanoreactor fabrication by electrospinning for sustainable catalysis.

An efficient and economical electrocatalyst as kinetic support is key to electrochemical reactions. For this reason, chemists have been working to investigate the basic changing of chemical principles when the system is confined in limited space with nanometer-scale dimensions or sub-microliter volumes. Inspired by biological research, the design and construction of a closed reaction environment, namely the reactor, has attracted more and more interest in chemistry, biology, and materials science. In particular, nanoreactors became a high-profile rising star and different types of nanoreactors have been fabricated. Compared with the traditional particle nanoreactor, the one-dimensional (1D) carbon-based nanoreactor prepared by the electrospinning process has better electrolyte diffusion, charge transfer capabilities, and outstanding catalytic activity and selectivity than the traditional particle catalyst which has great application potential in various electrochemical catalytic reactions.

Unveiling the dynamic active site of defective carbon-based electrocatalysts for hydrogen peroxide production.

Active sites identification in metal-free carbon materials is crucial for developing practical electrocatalysts, but resolving precise configuration of active site remains a challenge because of the elusive dynamic structural evolution process during reactions. Here, we reveal the dynamic active site identification process of oxygen modified defective graphene. First, the defect density and types of oxygen groups were precisely manipulated on graphene, combined with electrocatalytic performance evaluation, revealing a previously overlooked positive correlation relationship between the defect density and the 2 e- oxygen reduction performance. An electrocatalytic-driven oxygen groups redistribution phenomenon was observed, which narrows the scope of potential configurations of the active site. The dynamic evolution processes are monitored via multiple in-situ technologies and theoretical spectra simulations, resolving the configuration of major active sites (carbonyl on pentagon defect) and key intermediates (*OOH), in-depth understanding the catalytic mechanism and providing a research paradigm for metal-free carbon materials.

Quasi-Three-Dimensional Cyclotriphosphazene-Based Covalent Organic Framework Nanosheet for Efficient Oxygen Reduction.

Metal-free carbon-based materials are considered as promising oxygen reduction reaction (ORR) electrocatalysts for clean energy conversion, and their highly dense and exposed carbon active sites are crucial for efficient ORR. In this work, two unique quasi-three-dimensional cyclotriphosphazene-based covalent organic frameworks (Q3CTP-COFs) and their nanosheets were successfully synthesized and applied as ORR electrocatalysts. The abundant electrophilic structure in Q3CTP-COFs induces a high density of carbon active sites, and the unique bilayer stacking of [6 + 3] imine-linked backbone facilitates the exposure of active carbon sites and accelerates mass diffusion during ORR. In particular, bulk Q3CTP-COFs can be easily exfoliated into thin COF nanosheets (NSs) due to the weak interlayer π-π interactions. Q3CTP-COF NSs exhibit highly efficient ORR catalytic activity (half-wave potential of 0.72 V vs. RHE in alkaline electrolyte), which is one of the best COF-based ORR electrocatalysts reported so far. Furthermore, Q3CTP-COF NSs can serve as a promising cathode for Zn-air batteries (delivered power density of 156 mW cm-2 at 300 mA cm-2). This judicious design and accurate synthesis of such COFs with highly dense and exposed active sites and their nanosheets will promote the development of metal-free carbon-based electrocatalysts.

Controlling the terminal layer atom of InTe for enhanced electrochemical oxygen evolution reaction and hydrogen evolution reaction performance.

Herein, we report the method of molecular-beam-epitaxial growth (MBE) for precisely regulating the terminal surface with different exposed atoms on indium telluride (InTe) and studied the electrocatalytic performances toward hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). The improved performances result from the exposed In or Te atoms cluster, which affects the conductivity and active sites. This work provides insights into the comprehensive electrochemical attributes of layered indium chalcogenides and exhibits a new route for catalyst synthesis.

Facile and Scalable Mechanochemical Synthesis of Defective MoS2 with Ru Single Atoms Toward High-Current-Density Hydrogen Evolution.

Designing a facile strategy to prepare catalysts with highly active sites are challenging for large-scale implementation of electrochemical hydrogen production. Herein, a straightforward and eco-friendly method by high-energy mechanochemical ball milling for mass production of atomic Ru dispersive in defective MoS2 catalysts (Ru1 @D-MoS2 ) is developed. It is found that single atomic Ru doping induces the generation of S vacancies, which can break the electronic neutrality around Ru atoms, leading to an asymmetrical distribution of electrons. It is also demonstrated that the Ru1 @D-MoS2 exhibits superb alkaline hydrogen evolution enhancement, possibly attributing to this electronic asymmetry. The overpotential required to deliver a current density of 10 mA cm-2 is as low as 107 mV, which is much lower than that of commercial MoS2 (C-MoS2 , 364 mV). Further density functional theory (DFT) calculations also support that the vacancy-coupled single Ru enables much higher electronic distribution asymmetry degree, which could regulate the adsorption energy of intermediates, favoring the water dissociation and the adsorption/desorption of H*. Besides, the long-term stability test under 500 mA cm-2 further confirms the robust performance of Ru1 @D-MoS2 . Our strategy provides a promising and practical way towards large-scale preparation of advanced HER catalysts for commercial applications.

Defects in Carbon-Based Materials for Electrocatalysis: Synthesis, Recognition, and Advances.

ConspectusOwing to climate change and over-reliance on fossil fuels, the study and development of sustainable energy is of essential importance in the next few decades. In recent years, rapid advances have been witnessed in various power to gas electrocatalysis technologies including oxygen reduction reaction (ORR), oxygen evolution reaction (OER), and hydrogen evolution reaction (HER) for realizing the target of blue planet with carbon neutrality. Nevertheless, practical applications with superior performance and affordable cost are largely limited by the electrode materials because the reactions are regularly driven by precious metals such as platinum (Pt) or iridium (Ir) based catalysts. Therefore, it is of significance to develop novel electrocatalysts with high electroactivity and limited cost for boosting the commercialization of green hydrogen technology.Since nitrogen-doped carbon nanotubes were first reported for enhanced ORR performance in 2009, the exploitation of carbon-based metal-free catalysts (CMFCs) as potential replacements for the precious metal electrocatalysts has become an attractive research field. To date, great progress has been made in developing new dopant strategies for CMFCs; however, the details of the catalytic mechanism and identification of active sites remain unclear, owing to the complexity in controlling the dopants and their homogeneity in carbon-based materials. To tackle this issue, our group has presented a series of works on defects catalyzing electrochemical reactions and proposed a defect catalysis mechanism since 2015. This theory is now widely accepted by the research community and has become a very important area in electrocatalysis worldwide.In this Account, we first present the defect theory for the reasonable design of defective carbon-based materials (DCMs) and subsequently summarize our previous works on the state-of-the-art defect engineering strategies to design DCMs possessing high activity, with the particular emphasis on the conjunction between defect structures and electrochemical performances. We also categorize recent defect modulation approaches on active sites in DCMs as well as showcase the advanced characterization techniques to confirm the types and densities of defects in DCMs. Finally, several perspectives on the challenges and future research opportunities of this exciting field are proposed. Remarkably, rapid advances of DCMs possessing both high electrochemical activities and low cost as a new generation of electrode materials may greatly facilitate the deployment of sustainable energy infrastructures.

Improved feed forward with bald eagle search for conjunctive water management in deficit region.

Due to increasing requirements on water resources and a lower recharge rate, the farming seasons are a vital season for the management of groundwater and surface water resource management. This condition necessitates the use of combined water distribution to meet the full water requirements. Analysis of existing surface water resources and related restrictions, this research suggested an algorithm for aquifer stabilization and fulfilling optimum water requirements. To manage the optimum withdrawals and the subsequent drop, this technique first employed the MODFLOW model for simulating the water levels. Next, an improved feed-forward neural network (IFFNN) was combined with an optimization method to create a machine learning (ML) framework. During the last phase, the findings of the optimized connectives approach as well as the relevant fields technologies to determine using improved bald eagle search with least square SVM(IBES-LSSVM) method that predicted the level of water deficit for every period, especially during farming seasons. This approach is based on an improved bald eagle search (IBES) optimization technique for finding the best settings for a least-squares support vector machine (LSSVM). The findings revealed that between 2005 and 2020, the year with the biggest water deficit was 2018 when only roughly 64 percent of water need was satisfied by groundwater (69 percent) and surface water (64 percent) (33 percent). The water depth may have risen by around 0.7 m during the study period if the optimum model had been used. The outcome of this research will help the management forecast future water shortages and make smarter water strategic choices.

Three-dimensional microporous and mesoporous covalent organic frameworks based on cubic building units.

Covalent organic frameworks (COFs) have attracted extensive interest due to their unique structures and various applications. However, structural diversities are still limited, which greatly restricts the development of COF materials. Herein, we report two unusual cubic (8-connected) building units and their derived 3D imine-linked COFs with bcu nets, JUC-588 and JUC-589. Owing to these unique building blocks with different sizes, the obtained COFs can be tuned to be microporous or mesoporous structures with high surface areas (2728 m2 g-1 for JUC-588 and 2482 m2 g-1 for JUC-589) and promising thermal and chemical stabilities. Furthermore, the high selectivity of CO2/N2 and CO2/CH4, excellent H2 uptakes, and efficient dye adsorption are observed. This research thus provides a general strategy for constructing stable 3D COF architectures with adjustable pores via improving the valency of rigid building blocks.

Defective Fe Metal-Organic Frameworks Enhance Metabolic Profiling for High-Accuracy Diagnosis of Human Cancers.

Cancers heavily threaten human life; therefore, a high-accuracy diagnosis is vital to protect human beings from the suffering of cancers. While biopsies and imaging methods are widely used as current technologies for cancer diagnosis, a new detection platform by metabolic analysis is expected due to the significant advantages of fast, simple, and cost-effectiveness with high body tolerance. However, the signal of molecule biomarkers is too weak to acquire high-accuracy diagnosis. Herein, precisely engineered metal-organic frameworks for laser desorption/ionization mass spectrometry, allowing favorable charge transfer within the molecule-substrate interface and mitigated thermal dissipation by adjusting the phonon scattering with metal nodes, are developed. Consequently, a surprising signal enhancement of ≈10 000-fold is achieved, resulting in diagnosis of three major cancers (liver/lung/kidney cancer) with area-under-the-curve of 0.908-0.964 and accuracy of 83.2%-90.6%, which promises a universal detection tool for large-scale clinical diagnosis of human cancers.

Single Carbon Vacancy Traps Atomic Platinum for Hydrogen Evolution Catalysis.

The coordinated configuration of atomic platinum (Pt) has always been identified as an active site with high intrinsic activity for hydrogen evolution reaction (HER). Herein, we purposely synthesize single vacancies in a carbon matrix (defective graphene) that can trap atomic Pt to form the Pt-C3 configuration, which gives exceptionally high reactivity for HER in both acidic and alkaline solutions. The intrinsic activity of Pt-C3 site is valued with a turnover frequency (TOF) of 26.41 s-1 and mass activity of 26.05 A g-1 at 100 mV, respectively, which are both nearly 18 times higher than those of commercial 20 wt % Pt/C. It is revealed that the optimal coordination Pt-C3 has a stronger electron-capture ability and lower Gibbs free energy difference (ΔG), resulting in promoting the reduction of adsorbed H+ and the acceleration of H2 desorption, thus exhibiting the extraordinary HER activity. This work provides a new insight on the unique coordinated configuration of dispersive atomic Pt in defective C matrix for superior HER performance.

Controlled Asymmetric Charge Distribution of Active Centers in Conjugated Polymers for Oxygen Reduction.

Active center reconstruction is essential for high performance oxygen reduction reaction (ORR) electrocatalysts. Usually, the ORR activity stems from the electronic environment of active sites by charge redistribution. We introduce an asymmetry strategy to adjust the charge distribution of active centers by designing conjugated polymer (CP) catalysts with different degrees of asymmetry. We synthesized asymmetric backbone CP (asy-PB) by modifying B←N coordination bonds and asymmetric sidechain CP (asy-PB-A) with different alkyl chain lengths. Both CPs with backbone and sidechain asymmetry exhibit superior ORR performance to their symmetric counterparts (sy-P and sy-PB). The asy-PB with greater asymmetry shows higher catalytic activity than asy-PB-A with relatively smaller asymmetry. DFT calculations reveal that the increased dipole moment and non-uniform charge distribution caused by asymmetric structure endows the center carbon atom of bipyridine with efficient catalytic activity.

MicroRNA differential expression spectrum and microRNA-125a-5p inhibition of laryngeal cancer cell proliferation.

[This retracts the article DOI: 10.3892/etm.2017.4685.].

Defect engineering and characterization of active sites for efficient electrocatalysis.

Electrocatalysis plays a decisive role in various energy-related applications. Engineering the active sites of electrocatalysts is an important aspect to promote their catalytic performance. In particular, defect engineering provides a feasible and efficient approach to improve the intrinsic activities and increase the number of active sites in electrocatalysts. In this review, recent investigations on defect engineering of a wide range of electrocatalysts such as metal-free carbon materials, transition metal oxides, transition metal dichalcogenides and metal-organic frameworks (MOFs) will be summarized. Different defect creation strategies will be outlined, for example, heteroatom doping and removal, plasma irradiation, hydrogenation, amorphization, phase transition and reduction treatment. In addition, we will overview the commonly used advanced characterization techniques that could confirm the existence and identify the detailed structures, types and concentration of defects in electrocatalysts. The defect characterization tools are beneficial for gaining an in-depth understanding of defects on electrocatalysis and thus could reveal the structure-performance relationship. Finally, the major challenges and future development directions on defect engineering of electrocatalysts will be discussed.

Sulfur-Modified Oxygen Vacancies in Iron-Cobalt Oxide Nanosheets: Enabling Extremely High Activity of the Oxygen Evolution Reaction to Achieve the Industrial Water Splitting Benchmark.

The oxygen vacancies of defective iron-cobalt oxide (FeCoOx -Vo) nanosheets are modified by the homogeneously distributed sulfur (S) atoms. S atoms can not only effectively stabilize oxygen vacancies (Vo), but also form the Co-S coordination with Co active site in the Vo, which can modulate the electronic structure of the active site, enabling FeCoOx -Vo-S to exhibit much superior OER activity. FeCoOx -Vo-S exhibits a mass activity of 2440.0 A g-1 at 1.5 V vs. RHE in 1.0 m KOH, 25.4 times higher than that of RuO2 . The Tafel slope is as low as 21.0 mV dec-1 , indicative of its excellent charge transfer rate. When FeCoOx -Vo-S (anode catalyst) is paired with the defective CoP3 /Ni2 P (cathode catalyst) for overall water splitting, current densities of as high as 249.0 mA cm-2 and 406.0 mA cm-2 at a cell voltage of 2.0 V and 2.3 V, respectively, can be achieved.

Gradient-Concentration Design of Stable Core-Shell Nanostructure for Acidic Oxygen Reduction Electrocatalysis.

Manipulating the surface structure of electrocatalysts at the atomic level is of primary importance to simultaneously achieve the activity and stability dual-criteria in oxygen reduction reaction (ORR) for proton exchange membrane fuel cells. Here, a durable acidic ORR electrocatalyst with the "defective-armored" structure of Pt shell and Pt-Ni core nanoparticle decorated on graphene (Pt-Ni@PtD /G) using a facile and controllable galvanic replacement reaction to generate gradient distribution of Pt-Ni composition from surface to interior, followed by a partial dealloying approach, leaching the minor nickel atoms on the surface to generate defective Pt skeleton shell, is reported. The Pt-Ni@PtD /G catalyst shows impressive performance for ORR in acidic (0.1 m HClO4 ) electrolyte, with a high mass activity of threefold higher than that of Pt/C catalyst owing to the tuned electronic structure of locally concave Pt surface sites through synergetic contributions of Pt-Ni core and defective Pt shell. More importantly, the electrochemically active surface areas still retain 96% after 20 000 potential cycles, attributing to the Pt atomic shell acting as the protective "armor" to prevent interior Ni atoms from further dissolution during the long-term operation.