A climax in the development of cost-effective and high-efficiency transition metal-based electrocatalysts has been witnessed recently for sustainable energy and related conversion technologies. In this regard, structure-activity relationships based on several descriptors have already been proposed to rationally design electrocatalysts. However, the dynamic reconstruction of the surface structures and compositions of catalysts during electrocatalytic water oxidation, especially during the anodic oxygen evolution reaction (OER), complicate the streamlined prediction of the catalytic activity. With the achievements in operando and in situ techniques, it has been found that electrocatalysts undergo surface reconstruction to form the actual active species in situ accompanied with an increase in their oxidation state during OER in alkaline solution. Accordingly, a thorough understanding of the surface reconstruction process plays a critical role in establishing unambiguous structure-composition-property relationships in pursuit of high-efficiency electrocatalysts. However, several issues still need to be explored before high electrocatalytic activities can be realized, as follows: (1) the identification of initiators and pathways for surface reconstruction, (2) establishing the relationships between structure, composition, and electrocatalytic activity, and (3) the rational manipulation of in situ catalyst surface reconstruction. In this review, the recent progress in the surface reconstruction of transition metal-based OER catalysts including oxides, non-oxides, hydroxides and alloys is summarized, emphasizing the fundamental understanding of reconstruction behavior from the original precatalysts to the actual catalysts based on operando analysis and theoretical calculations. The state-of-the-art strategies to tailor the surface reconstruction such as substituting/doping with metals, introducing anions, incorporating oxygen vacancies, tuning morphologies and exploiting plasmonic/thermal/photothermal effects are then introduced. Notably, comprehensive operando/in situ characterization together with computational calculations are responsible for unveiling the improvement mechanism for OER. By delivering the progress, strategies, insights, techniques, and perspectives, this review will provide a comprehensive understanding of the surface reconstruction in transition metal-based OER catalysts and future guidelines for their rational development.

Recent advances in activating surface reconstruction for the high-efficiency oxygen evolution reaction.

Heterogeneous catalysis plays an important role in modern industries. Exploring catalysts with high efficiency, low-cost and high stability is an important issue for the research of heterogeneous c...

Defect chemistry in heterogeneous catalysis: recognition, understanding and utilization

The development of efficient and low-cost electrocatalysts toward the oxygen evolution reaction (OER) is critical for improving the efficiency of several electrochemical energy conversion and storage devices. Here, we report an elaborate design and synthesis of porous Co-based trimetallic spinel oxide nanoboxes (NiCo2-x Fex O4 NBs) by a novel metal-organic framework engaged strategy, which involves chemical etching, cation exchange, and subsequent thermal oxidation processes. Owing to the structural and compositional advantages, the optimized trimetallic NiCo2-x Fex O4 NBs (x is about 0.117) deliver superior electrocatalytic performance for OER with an overpotential of 274 mV at 10 mA cm-2 , a small Tafel slope of 42 mV dec-1 , and good stability in alkaline electrolyte, which is much better than that of Co-based bi/monometallic spinel oxides and even commercial RuO2 .

Trimetallic Spinel NiCo2-xFexO4 Nanoboxes for Highly Efficient Electrocatalytic Oxygen Evolution.

Developing efficient and stable earth-abundant electrocatalysts for acidic oxygen evolution reaction is the bottleneck for water splitting using proton exchange membrane electrolyzers. Here, we show that nanocrystalline CeO2 in a Co3O4/CeO2 nanocomposite can modify the redox properties of Co3O4 and enhances its intrinsic oxygen evolution reaction activity, and combine electrochemical and structural characterizations including kinetic isotope effect, pH- and temperature-dependence, in situ Raman and ex situ X-ray absorption spectroscopy analyses to understand the origin. The local bonding environment of Co3O4 can be modified after the introduction of nanocrystalline CeO2, which allows the CoIII species to be easily oxidized into catalytically active CoIV species, bypassing the potential-determining surface reconstruction process. Co3O4/CeO2 displays a comparable stability to Co3O4 thus breaks the activity/stability tradeoff. This work not only establishes an efficient earth-abundant catalysts for acidic oxygen evolution reaction, but also provides strategies for designing more active catalysts for other reactions.

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Modifying redox properties and local bonding of Co3O4 by CeO2 enhances oxygen evolution catalysis in acid

Reconstruction induced by external environment (such as applied voltage bias and test electrolytes) changes catalyst component and catalytic behaviors. Investigations of complete reconstruction in energy conversion recently receive intensive attention, which promote the targeted design of top-performance materials with maximum component utilization and good stability. However, the advantages of complete reconstruction, its design strategies, and extensive applications have not achieved the profound understandings and summaries it deserves. Here, this review systematically summarizes several important advances in complete reconstruction for the first time, which includes 1) fundamental understandings of complete reconstruction, the characteristics and advantages of completely reconstructed catalysts, and their design principles, 2) types of reconstruction-involved precatalysts for oxygen evolution reaction catalysis in wide pH solution, and origins of limited reconstruction degree as well as design strategies/principles toward complete reconstruction, 3) complete reconstruction for novel material synthesis and other electrocatalysis fields, and 4) advanced in situ/operando or multiangle/level characterization techniques to capture the dynamic reconstruction processes and real catalytic contributors. Finally, the existing major challenges and unexplored/unsolved issues on studying the reconstruction chemistry are summarized, and an outlook for the further development of complete reconstruction is briefly proposed. This review will arouse the attention on complete reconstruction materials and their applications in diverse fields.

Comprehensive Understandings into Complete Reconstruction of Precatalysts: Synthesis, Applications, and Characterizations.

The exact role of a defect structure on transition metal compounds for electrocatalytic oxygen evolution reaction (OER), which is a very dynamic process, remains unclear. Studying the structure-activity relationship of defective electrocatalysts under operando conditions is crucial for understanding their intrinsic reaction mechanism and dynamic behavior of defect sites. Co3O4 with rich oxygen vacancy (VO) has been reported to efficiently catalyze OER. Herein, we constructed pure spinel Co3O4 and VO-rich Co3O4 as catalyst models to study the defect mechanism and investigate the dynamic behavior of defect sites during the electrocatalytic OER process by various operando characterizations. Operando electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV) implied that the VO could facilitate the pre-oxidation of the low-valence Co (Co2+, part of which was induced by the VO to balance the charge) at a relatively lower applied potential. This observation confirmed that the VO could initialize the surface reconstruction of VO-Co3O4 prior to the occurrence of the OER process. The quasi-operando X-ray photoelectron spectroscopy (XPS) and operando X-ray absorption fine structure (XAFS) results further demonstrated the oxygen vacancies were filled with OH• first for VO-Co3O4 and facilitated pre-oxidation of low-valence Co and promoted reconstruction/deprotonation of intermediate Co-OOH•. This work provides insight into the defect mechanism in Co3O4 for OER in a dynamic way by observing the surface dynamic evolution process of defective electrocatalysts and identifying the real active sites during the electrocatalysis process. The current finding would motivate the community to focus more on the dynamic behavior of defect electrocatalysts.

Operando Identification of the Dynamic Behavior of Oxygen Vacancy-Rich Co3O4 for Oxygen Evolution Reaction.

Bilayer tungsten diselenide transistors with on-state currents exceeding 1.5 milliamperes per micrometre

Polarization is a common and unique phenomenon in nature, which reveals more camouflage features of objects. However, current polarization-perceptual devices based on conventional physical architectures face enormous challenges for high-performance computation due to the traditional von Neumann bottleneck. In this work, a novel polarization-perceptual neuro-transistor with reconfigurable anisotropic vision is proposed based on a two-dimensional ReS2 phototransistor. The device exhibits excellent photodetection ability and superior polarization sensitivity due to its direct band gap semiconductor property and strong anisotropic crystal structure, respectively. The fascinating polarization-sensitive neuromorphic behavior, such as polarization memory consolidation and reconfigurable visual imaging, are successfully realized. In particular, the regulated polarization responsivity and dichroic ratio are successfully emulated through our artificial compound eyes. More importantly, two intriguing polarization-perceptual applications for polarized navigation with reconfigurable adaptive learning abilities and three-dimensional visual polarization imaging are also experimentally demonstrated. The proposed device may provide a promising opportunity for future polarization perception systems in intelligent humanoid robots and autonomous vehicles.

Polarization-perceptual anisotropic two-dimensional ReS2 neuro-transistor with reconfigurable neuromorphic vision.

Visual adaptation allows organisms to accurately perceive the external world even in dramatically changing environments, from dim starlight to bright sunlight. In particular, polarization‐sensitive visual adaptation can effectively process the polarized visual information that is ubiquitous in nature. However, such an intriguing characteristic still remains a great challenge in semiconductor devices. Herein, a novel porous metal–organic‐framework phototransistor with anisotropic‐ReS2‐based heterojunction is demonstrated for polarization‐sensitive visual adaptation emulation. The device exhibits intriguing polarized sensitivity and an adaptive ability due to its strong anisotropic and trapping–detrapping characteristics, respectively. A series of polarization‐sensitive neuromorphic behaviors like polarization‐perceptual excitatory postsynaptic current, multimode adjustable dichroic ratio and reconfigurable sensory adaption, are experimentally demonstrated through this porous heterojunction phototransistor. More importantly, with the polarization–electricity cooperation strategy, advanced polarization‐sensitive visual adaptation with strong bottom‐gate control and environment dependence is successfully realized. These results represent a significant step toward the new generation of intelligent visual perception systems in autonomous navigation and human–machine interaction, etc.

Porous Metal–Organic Framework/ReS2 Heterojunction Phototransistor for Polarization‐Sensitive Visual Adaptation Emulation

The suspended metallic nanostructures with tiny gaps have certain advantages in surface-enhanced Raman scattering (SERS) due to the coaction of the tiny metallic nanogaps and the substrate-decoupled electromagnetism resonant modes. In this study, we used the lithographic HSQ/PMMA electron-beam bilayer resist exposure combined with a deposition-induced nanogap-narrowing process to define elevated suspended metallic nanodimers with tiny gaps for surface-enhanced Raman spectroscopy detection. By adjusting the deposited metal thickness, the metallic dimers with sub-10 nm gaps can be reliably obtained. These dimers with tunable nanogaps successfully served as excellent SERS substrates, exhibiting remarkable high-sensitivity detection ability for crystal violet molecules. Systematic experiments and simulations were conducted to explain the origin of the improved SERS performance. The results showed that the 3D elevated suspended metallic dimers could achieve a higher SERS enhancement factor than the metallic dimers on HSQ pillars and a common Si substrate, demonstrating that this kind of suspended metallic dimer is a promising route for high-sensitive SERS detection and other plasmonic applications.

Zhiwen Shu

Papers

Operando Identification of the Dynamic Behavior of Oxygen Vacancy-Rich Co3O4 for Oxygen Evolution Reaction.

Bilayer tungsten diselenide transistors with on-state currents exceeding 1.5 milliamperes per micrometre

Polarization-perceptual anisotropic two-dimensional ReS2 neuro-transistor with reconfigurable neuromorphic vision.

Porous Metal–Organic Framework/ReS2 Heterojunction Phototransistor for Polarization‐Sensitive Visual Adaptation Emulation

Suspended 3D metallic dimers with sub-10 nm gap for high-sensitive SERS detection