Local hydroxide ion enrichment at the inner surface of lacunaris perovskite nanotubes facilitates the oxygen evolution reaction.

Numerous strategies have been devised to optimize the intrinsic activity of perovskite oxides for the oxygen evolution reaction (OER). However, conventional synthetic routes typically yield limited numbers of active sites and low mass activities. More critically, the sluggish mass transfer poses a huge challenge, particularly under high polarization conditions, which impedes the overall reaction kinetics. Herein, lacunaris La0.5Pr0.25Ba0.25Co0.8Ni0.2O3-δ nanotubes (LPBCN-NTs) were prepared via electrospinning and post-annealing, which exhibited a small overpotential of 358.8 mV at 10 mA cm-2 and a lower Tafel slope of 71.46 mV dec-1, superior to the values for the same stoichiometric LPBCN nanoparticles and solid nanofibers, state-of-the-art counterparts and commercial IrO2. Density functional theory calculations revealed that the surface oxygen vacancies in LPBCN-NTs significantly lowered the OH- adsorption energy, while finite element analysis indicated that the precisely constructed lacunaris NT structure enriched the OH- concentration at its inner surface by an order of magnitude, both of which collectively resulted in accelerated OER kinetics. This study clarifies the underlying mechanism of how the lacunaris nanotubular architecture and the surface oxygen vacancies of perovskite oxides affect heterocatalysis, which undoubtedly paves the way to handling the long-standing issues of sluggish mass transfer rates and poor intrinsic catalytic activity.

Strong effect-correlated electrochemical CO2 reduction.

Electrochemical CO2 reduction (ECR) holds great potential to alleviate the greenhouse effect and our dependence on fossil fuels by integrating renewable energy for the electrosynthesis of high-value fuels from CO2. However, the high thermodynamic energy barrier, sluggish reaction kinetics, inadequate CO2 conversion rate, poor selectivity for the target product, and rapid electrocatalyst degradation severely limit its further industrial-scale application. Although numerous strategies have been proposed to enhance ECR performances from various perspectives, scattered studies fail to comprehensively elucidate the underlying effect-performance relationships toward ECR. Thus, this review presents a comparative summary and a deep discussion with respect to the effects strongly-correlated with ECR, including intrinsic effects of materials caused by various sizes, shapes, compositions, defects, interfaces, and ligands; structure-induced effects derived from diverse confinements, strains, and fields; electrolyte effects introduced by different solutes, solvents, cations, and anions; and environment effects induced by distinct ionomers, pressures, temperatures, gas impurities, and flow rates, with an emphasis on elaborating how these effects shape ECR electrocatalytic activities and selectivity and the underlying mechanisms. In addition, the challenges and prospects behind different effects resulting from various factors are suggested to inspire more attention towards high-throughput theoretical calculations and in situ/operando techniques to unlock the essence of enhanced ECR performance and realize its ultimate application.

Oxygen Vacancy-Driven Heterointerface Breaks the Linear-Scaling Relationship of Intermediates toward Electrocatalytic CO2 Reduction.

Smart metal-metal oxide heterointerface construction holds promising potentials to endow an efficient electron redistribution for electrochemical CO2 reduction reaction (CO2RR). However, inhibited by the intrinsic linear-scaling relationship, the binding energies of competitive intermediates will simultaneously change due to the shifts of electronic energy level, making it difficult to exclusively tailor the binding energies to target intermediates and the final CO2RR performance. Nonetheless, creating specific adsorption sites selective for target intermediates probably breaks the linear-scaling relationship. To verify it, Ag nanoclusters were anchored onto oxygen vacancy-rich CeO2 nanorods (Ag/OV-CeO2) for CO2RR, and it was found that the oxygen vacancy-driven heterointerface could effectively promote CO2RR to CO across the entire potential window, where a maximum CO Faraday efficiency (FE) of 96.3% at -0.9 V and an impressively high CO FE of over 62.3% were achieved at a low overpotential of 390 mV within a flow cell. The experimental and computational results collectively suggested that the oxygen vacancy-driven heterointerfacial charge spillover conferred an optimal electronic structure of Ag and introduced additional adsorption sites exclusively recognizable for *COOH, which, beyond the linear-scaling relationship, enhanced the binding energy to *COOH without hindering *CO desorption, thus resulting in the efficient CO2RR to CO.

Visualizing Electrochemical CO2 Conversion via the Emerging Scanning Electrochemical Microscope: Fundamentals, Applications and Perspectives.

With the rapid development and maturity of electrochemical CO2 conversion involving cathodic CO2 reduction reaction (CO2RR) and anodic oxygen evolution reaction (OER), conventional ex situ characterizations gradually fall behind in detecting real-time products distribution, tracking intermediates, and monitoring structural evolution, etc. Nevertheless, advanced in situ techniques, with intriguing merits like good reproducibility, facile operability, high sensitivity, and short response time, can realize in situ detection and recording of dynamic data, and observe materials structural evolution in real time. As an emerging visual technique, scanning electrochemical microscope (SECM) presents local electrochemical signals on various materials surface through capturing micro-current caused by reactants oxidation and reduction. Importantly, SECM holds particular potentials in visualizing reactive intermediates at active sites and obtaining instantaneous morphology evolution images to reveal the intrinsic reactivity of active sites. Therefore, this review focuses on SECM fundamentals and its specific applications toward CO2RR and OER, mainly including electrochemical behavior observation on local regions of various materials, target products and onset potentials identification in real-time, reaction pathways clarification, reaction kinetics exploration under steady-state conditions, electroactive materials screening and multi-techniques coupling for a joint utilization. This review undoubtedly provides a leading guidance to extend various SECM applications to other energy-related fields.

Perovskite Oxides Toward Oxygen Evolution Reaction: Intellectual Design Strategies, Properties and Perspectives.

Developing electrochemical energy storage and conversion devices (e.g., water splitting, regenerative fuel cells and rechargeable metal-air batteries) driven by intermittent renewable energy sources holds a great potential to facilitate global energy transition and alleviate the associated environmental issues. However, the involved kinetically sluggish oxygen evolution reaction (OER) severely limits the entire reaction efficiency, thus designing high-performance materials toward efficient OER is of prime significance to remove this obstacle. Among various materials, cost-effective perovskite oxides have drawn particular attention due to their desirable catalytic activity, excellent stability and large reserves. To date, substantial efforts have been dedicated with varying degrees of success to promoting OER on perovskite oxides, which have generated multiple reviews from various perspectives, e.g., electronic structure modulation and heteroatom doping and various applications. Nonetheless, the reviews that comprehensively and systematically focus on the latest intellectual design strategies of perovskite oxides toward efficient OER are quite limited. To bridge the gap, this review thus emphatically concentrates on this very topic with broader coverages, more comparative discussions and deeper insights into the synthetic modulation, doping, surface engineering, structure mutation and hybrids. More specifically, this review elucidates, in details, the underlying causality between the being-tuned physiochemical properties [e.g., electronic structure, metal-oxygen (M-O) bonding configuration, adsorption capacity of oxygenated species and electrical conductivity] of the intellectually designed perovskite oxides and the resulting OER performances, coupled with perspectives and potential challenges on future research. It is our sincere hope for this review to provide the scientific community with more insights for developing advanced perovskite oxides with high OER catalytic efficiency and further stimulate more exciting applications.

Emerging Nanomaterials toward Uranium Extraction from Seawater: Recent Advances and Perspectives.

Nuclear energy holds great potential to facilitate the global energy transition and alleviate the increasing environmental issues due to its high energy density, stable energy output, and carbon-free emission merits. Despite being limited by the insufficient terrestrial uranium reserves, uranium extraction from seawater (UES) can offset the gap. However, the low uranium concentration, the complicated uranium speciation, the competitive metal ions, and the inevitable marine interference remarkably affect the kinetics, capacity, selectivity, and sustainability of UES materials. To date, massive efforts have been made with varying degrees of success to pursue a desirable UES performance on various nanomaterials. Nevertheless, comprehensive and systematic coverage and discussion on the emerging UES materials presenting the fast-growing progress of this field is still lacking. This review thus challenges this position and emphatically focuses on this topic covering the current mainstream UES technologies with the emerging UES materials. Specifically, this review elucidates the causality between the physiochemical properties of UES materials induced by the intellectual design strategies and the UES performances and further dissects the relationships of materials-properties-activities and the corresponding mechanisms in depth. This review is envisaged to inspire innovative ideas and bring technical solutions for developing technically and economically viable UES materials.

Oxygen vacancy-mediated peroxydisulfate activation and singlet oxygen generation toward 2,4-dichlorophenol degradation on specific CuO1-x nanosheets.

Durable and stable removal of 2,4-dichlorophenpl (2,4-DCP) by CuO1-x nanosheets is reported. CuO1-x nanosheets were fabricated by a simple defect engineering strategy and greatly increased the efficiency of peroxydisulfate (PDS) activation to improve 2,4-DCP removal by introducing abundant oxygen vacancy (Vo) to produce an electron-rich surface. Results showed that CuO1-x nanosheets exposed more Vo as active sites for PDS activation as compared with that of CuO nanoparticles, giving rise to dramatic enhancement of catalytic performance with ultrahigh reaction rate that is qualified for serving in flow filtration system, completely degrading 100 mg L-1 of 2,4-DCP within 3 s of residence time. Besides, experimental studies confirmed that 1O2 generated by Vo - mediated PDS activation plays the dominate role in the degradation of contaminants. Relative to the previously reported CuO/PDS systems, the obtained CuO1-x nanosheets demonstrated 2.7 times higher specific PDS activity and 67 times higher specific CuO activity for 2,4-DCP removal. Our study not only improves the fundamental understanding of active sites in morphologically tunable metal oxides but also proposes a guideline for future research and engineering application of persulfate.

Theory-Guided Modulation of Optimal Silver Nanoclusters toward Efficient CO2 Electroreduction.

Electrochemical CO2 reduction reaction (CO2RR), when powered with intermittent but renewable energies, holds an attractive potential to close the anthropogenic carbon cycle through efficiently converting the exorbitantly discharged CO2 to value-added fuels and/or chemicals and consequently reduce the greenhouse gas emission. Through systematically integrating the density functional theory calculations, the modeling statistics of various proportions of CO2RR-preferred electroactive sites, and the theoretical work function results, it is found that the crystallographically unambiguous Ag nanoclusters (NCs) hold a high possibility to enable an outstanding CO2RR performance, particularly at an optimal size of around 2 nm. Motivated by this, homogeneously well-distributed ultrasmall Ag NCs with an average size of ∼2 nm (2 nm Ag NCs) were thus synthesized to electrochemically promote CO2RR, and the results demonstrate that the 2 nm Ag NCs are able to achieve a significantly larger CO partial current density [j(CO)], an impressively higher CO Faraday efficiency of over 93.8%, and a lower onset overpotential (η) of 146 mV as well as a remarkably higher energy efficiency of 62.8% and a superior stability of 45 h as compared to Ag nanoparticles (Ag NPs) and bulk Ag. Both theoretical computations and experimental results clearly and persuasively demonstrate an impressive promotion effect of the crystallographically explicit atomic structure for electrochemically reducing CO2 to CO, which exemplifies a novel design approach to more benchmark metal-based platforms for advancing the practically large-scale CO2RR application.

Interface-Induced Electrocatalytic Enhancement of CO2 -to-Formate Conversion on Heterostructured Bismuth-Based Catalysts.

Electrochemical CO2 reduction reaction (CO2 RR) is a promising approach to convert CO2 to carbon-neutral fuels using external electric powers. Here, the Bi2 S3 -Bi2 O3 nanosheets possessing substantial interface being exposed between the connection of Bi2 S3 and Bi2 O3 are prepared and subsequently demonstrate to improve CO2 RR performance. The electrocatalyst shows formate Faradaic efficiency (FE) of over 90% in a wide potential window. A high partial current density of about 200 mA cm-2 at -1.1 V and an ultralow onset potential with formate FE of 90% are achieved in a flow cell. The excellent electrocatalytic activity is attributed to the fast-interfacial charge transfer induced by the electronic interaction at the interface, the increased number of active sites, and the improved CO2 adsorption ability. These collectively contribute to the faster reaction kinetics and improved selectivity and consequently, guarantee the superb CO2 RR performance. This study provides an appealing strategy for the rational design of electrocatalysts to enhance catalytic performance by improving the charge transfer ability through constructing a functional heterostructure, which enables interface engineering toward more efficient CO2 RR.

Hexagonal Zn Nanoplates Enclosed by Zn(100) and Zn(002) Facets for Highly Selective CO2 Electroreduction to CO.

Electrochemical reduction of CO2 to carbon-neutral fuels is a promising strategy for renewable energy conversion and storage. However, developing earth-abundant and cost-effective electrocatalysts with high catalytic activity and desirable selectivity for the target fuel is still challenging and imperative. Herein, hexagonal Zn nanoplates (H-Zn-NPs) enclosed by Zn(100) and Zn(002) facets were successfully synthesized and studied for their feasibility toward the CO2 reduction reaction (CO2RR). Compared with similarly sized Zn nanoparticles (S-Zn-NPs), the H-Zn-NPs exhibit remarkably enhanced current density, together with an improved CO faradaic efficiency (FE) of over 85% in a wide potential window, where a maximum FE of 94.2% is achieved. The enhancement in the CO2RR performance benefits from the substantial catalytically active sites introduced by the special architecture of H-Zn-NPs. Density functional theory calculations reveal that the exposed Zn(100) facets and edge sites on H-Zn-NPs are energetically favorable for CO2RR to CO, which directly result in an enhanced CO2RR performance. This study undoubtedly provides a straightforward approach to controlling the catalytic activity and selectivity of CO2RR through tuning the shape of Zn-based catalysts so as to maximize the percentage of exposed Zn(100) facets.

Bi2 O3 Nanosheets Grown on Multi-Channel Carbon Matrix to Catalyze Efficient CO2 Electroreduction to HCOOH.

Bi2 O3 nanosheets were grown on a conductive multiple channel carbon matrix (MCCM) for CO2 RR. The obtained electrocatalyst shows a desirable partial current density of ca. 17.7 mA cm-2 at a moderate overpotential, and it is highly selective towards HCOOH formation with Faradaic efficiency approaching 90 % in a wide potential window and its maximum value of 93.8 % at -1.256 V. It also exhibits a maximum energy efficiency of 55.3 % at an overpotential of 0.846 V and long-term stability of 12 h with negligible degradation. The superior performance is attributed to the synergistic contribution of the interwoven MCCM and the hierarchical Bi2 O3 nanosheets, where the MCCM provides an accelerated electron transfer, increased CO2 adsorption, and a high ratio of pyrrolic-N and pyridinic-N, while ultrathin Bi2 O3 nanosheets offer abundant active sites, lowered contact resistance and work function as well as a shortened diffusion pathway for electrolyte.

Achieving Efficient CO2 Electrochemical Reduction on Tunable In(OH)3-Coupled Cu2O-Derived Hybrid Catalysts.

Tunable In(OH)3-coupled Cu2O-derived hybrid catalysts are facilely synthesized to boost the selectivity and efficiency of the electrochemical CO2 reduction reaction (CO2RR). The maximum faradaic efficiency (FE) of 90.37% for CO production is achieved at -0.8 V versus reversible hydrogen electrode. The mechanistic discussion suggests that the composition-dependent synergistic effect results in the enhanced selectivity for CO on the hybrid catalyst. By increasing the concentration of the electrolyte, a dramatically enhanced current density of 40.17 mA cm-2 was achieved at -1.0 V in 0.7 M KHCO3. Furthermore, a KHCO3 electrolyte with high concentration promotes the selectivity of CO2RR over the low overpotential range. At a low overpotential of 290 mV, the increased FE for CO of 74.05% is obtained in 0.7 M KHCO3 as compared to that of 57.04% in 0.1 M KHCO3. Combining with the synergistic effect of the catalyst and the concentration effect of the electrolyte, the hybrid catalyst achieves high efficiency, high selectivity, and high stability for CO2RR.

Insights into the Interfacial Process in Electroless Ni-P Coating on Supercritical CO2 Transport Pipeline as Relevant to Carbon Capture and Storage.

To reduce the amount of greenhouse gas emissions and remedy related environmental damage, the research on carbon capture and storage (CCS) is gaining momentum and so is the search for a more effective way to control corrosion of pipeline steel used to transport impure supercritical (SC) CO2. Herein, we prepared an electroless high-phosphorus Ni-P coating and, for the first time, systematically explored the underlying mechanism of the interfacial process in applying Ni-P coating to protect pipeline steel that transports impure SC CO2. It is found that, benefiting from the formation of a protective surface film, Ni-P coating significantly mitigates the corrosion effects from SC CO2 and impurities (e.g., O2 and NO2), especially the synergistic effect of impurities. Concurrently, it effectively avoids the localized corrosion resulting from nonuniform adsorption of the aqueous phase. Although O2 and NO2 can degrade the coating through boosting water precipitation, deteriorating the water chemistry, and reducing the surface film protectiveness, the corrosion inhibition efficiency of Ni-P coating is invariably higher than 80%, independent of the varying causticity of SC CO2 streams, demonstrating that the coating has a superior stability toward corrosion attack. The as-prepared Ni-P coating undoubtedly holds great potential as an alternative for corrosion control of CO2 transport pipeline in the CCS industry. This work provides a new, feasible method to ensure the safe and efficient operation of CCS.

Efficient Electrochemical Reduction of CO2 to HCOOH over Sub-2†nm SnO2 Quantum Wires with Exposed Grain Boundaries.

Electrochemical reduction of CO2 could mitigate environmental problems originating from CO2 emission. Although grain boundaries (GBs) have been tailored to tune binding energies of reaction intermediates and consequently accelerate the CO2 reduction reaction (CO2 RR), it is challenging to exclusively clarify the correlation between GBs and enhanced reactivity in nanostructured materials with small dimension (<10 nm). Now, sub-2 nm SnO2 quantum wires (QWs) composed of individual quantum dots (QDs) and numerous GBs on the surface were synthesized and examined for CO2 RR toward HCOOH formation. In contrast to SnO2 nanoparticles (NPs) with a larger electrochemically active surface area (ECSA), the ultrathin SnO2 QWs with exposed GBs show enhanced current density (j), an improved Faradaic efficiency (FE) of over 80 % for HCOOH and ca. 90 % for C1 products as well as energy efficiency (EE) of over 50 % in a wide potential window; maximum values of FE (87.3 %) and EE (52.7 %) are achieved.

Shape-Dependent Electrocatalytic Reduction of CO2 to CO on Triangular Silver Nanoplates.

Electrochemical reduction of CO2 (CO2RR) provides great potential for intermittent renewable energy storage. This study demonstrates a predominant shape-dependent electrocatalytic reduction of CO2 to CO on triangular silver nanoplates (Tri-Ag-NPs) in 0.1 M KHCO3. Compared with similarly sized Ag nanoparticles (SS-Ag-NPs) and bulk Ag, Tri-Ag-NPs exhibited an enhanced current density and significantly improved Faradaic efficiency (96.8%) and energy efficiency (61.7%), together with a considerable durability (7 days). Additionally, CO starts to be observed at an ultralow overpotential of 96 mV, further confirming the superiority of Tri-Ag-NPs as a catalyst for CO2RR toward CO formation. Density functional theory calculations reveal that the significantly enhanced electrocatalytic activity and selectivity at lowered overpotential originate from the shape-controlled structure. This not only provides the optimum edge-to-corner ratio but also dominates at the facet of Ag(100) where it requires lower energy to initiate the rate-determining step. This study demonstrates a promising approach to tune electrocatalytic activity and selectivity of metal catalysts for CO2RR by creating optimal facet and edge site through shape-control synthesis.