Switch Volmer-Heyrovsky to Volmer-Tafel Pathway for Efficient Acidic Electrocatalytic Hydrogen Evolution by Correlating Pt Single Atoms with Clusters.

As cost-effective catalysts, platinum (Pt) single-atom catalysts (SACs) have attracted substantial attention. However, most studies indicate that Pt SACs in acidic hydrogen evolution reaction (HER) follow the slow Volmer-Heyrovsky (VH) mechanism instead of the fast kinetic Volmer-Tafel (VT) pathway. Here, this work propose that the VH mechanism in Pt SACs can be switched to the faster VT pathway for efficient HER by correlating Pt single atoms (SAs) with Pt clusters (Cs). Our calculations reveal that the correlation between Pt SAs and Cs significantly impacts the electronic structure of exposed Pt atoms, lowering the adsorption barrier for atomic hydrogen and enabling a faster VT mechanism. To validate these findings, this work purposely synthesize three catalysts: l-Pt@MoS2 , m-Pt@MoS2 and h-Pt@MoS2 with low, moderate, and high Pt-loading, having different distributions of Pt SAs and Cs. The m-Pt@MoS2 catalyst with properly correlating Pt SAs and Cs exhibits outstanding performance with an overpotential of 47 mV and Tafel slope of 32 mV dec-1 . Further analysis of the Tafel values confirms that the m-Pt@MoS2 sample indeed follows the VT reaction mechanism, aligning with the theoretical findings. This study offers a deep understanding of the synergistic mechanism, paving a way for designing novel-advanced catalysts.

Correlating Single-Atomic Ruthenium Interdistance with Long-Range Interaction Boosts Hydrogen Evolution Reaction Kinetics.

Correlated single-atom catalysts (c-SACs) with tailored intersite metal-metal interactions are superior to conventional catalysts with isolated metal sites. However, precise quantification of the single-atomic interdistance (SAD) in c-SACs is not yet achieved, which is essential for a crucial understanding and remarkable improvement of the correlated metal-site-governed catalytic reaction kinetics. Here, three Ru c-SACs are fabricated with precise SAD using a planar organometallic molecular design and π-π molecule-carbon nanotube confinement. This strategy results in graded SAD from 2.4 to 9.3 Å in the Ru c-SACs, wherein tailoring the Ru SAD into 7.0 Å generates an exceptionally high turnover frequency of 17.92 H2 s-1 and a remarkable mass activity of 100.4 A mg-1 under 50 and 100 mV overpotentials, respectively, which is superior to all the Ru-based catalysts reported previously. Furthermore, density functional theory calculations confirm that Ru SAD has a negative correlation with its d-band center owing to the long-range interactions induced by distinct local atomic geometries, resulting in an appropriate electrostatic potential and the highest catalytic activity on c-SACs with 7.0 Å Ru SAD. The present study promises an attractive methodology for experimentally quantifying the metal SAD to provide valuable insights into the catalytic mechanism of c-SACs.

Tuning Active Metal Atomic Spacing by Filling of Light Atoms and Resulting Reversed Hydrogen Adsorption-Distance Relationship for Efficient Catalysis.

Precisely tuning the spacing of the active centers on the atomic scale is of great significance to improve the catalytic activity and deepen the understanding of the catalytic mechanism, but still remains a challenge. Here, we develop a strategy to dilute catalytically active metal interatomic spacing (dM-M) with light atoms and discover the unusual adsorption patterns. For example, by elevating the content of boron as interstitial atoms, the atomic spacing of osmium (dOs-Os) gradually increases from 2.73 to 2.96 Å. More importantly, we find that, with the increase in dOs-Os, the hydrogen adsorption-distance relationship is reversed via downshifting d-band states, which breaks the traditional cognition, thereby optimizing the H adsorption and H2O dissociation on the electrode surface during the catalytic process; this finally leads to a nearly linear increase in hydrogen evolution reaction activity. Namely, the maximum dOs-Os of 2.96 Å presents the optimal HER activity (8 mV @ 10 mA cm-2) in alkaline media as well as suppressed O adsorption and thus promoted stability. It is believed that this novel atomic-level distance modulation strategy of catalytic sites and the reversed hydrogen adsorption-distance relationship can shew new insights for optimal design of highly efficient catalysts.

Recent Progress in Metal-Catalyzed Selective Oxidation of 5-Hydroxymethylfurfural into Furan-Based Value-Added Chemicals.

5-hydroxymethylfurfural (HMF), one of the most significant biomass-derived renewable resources, has been widely utilized to create furan-based value-added chemicals such as 2,5-diformylfuran (DFF), 5-hydroxymethyl-2-furancarboxylic acid (HMFCA), 5-formyl-2-furancarboxylic acid (FFCA), and 2,5-furan dicarboxylic acid (FDCA). Indeed, DFF, HMFCA and FFCA are key intermediate products during the oxidation of HMF to FDCA. Herein, this review aims to demonstrate the recent advances in metal-catalyzed oxidation of HMF into FDCA via two different reaction routes (HMF-DFF-FFCA-FDCA and HMF-HMFCA-FFCA-FDCA). All the four furan-based compounds are comprehensively discussed by the selective oxidation of HMF. Additionally, various metal catalysts, reaction conditions, and reaction mechanisms used to obtain the four different products are systematically reviewed. It is anticipated that this review will provide related researchers with new perspectives and speed up the development of this field.

Recent Advances in the Synthesis of MXene Quantum Dots.

Quantum dots (QDs) with ultrahigh surface-to-volume ratio, abundant edge active sites, forceful quantum confinement and other remarkable physio-chemical properties, have garnered considerable research interest. MXene QDs, as an emerging member of them, have also attracted wide attention in the last six years, and shown great achievements in many fields. This critical review systematically summarizes the various methods for synthesizing MXene QDs. The characteristics and corresponding applications of various MXene QDs are also presented. The advantages and disadvantages of various synthetic methods, and the limitations of corresponding MXene QDs are compared and highlighted. Finally, the challenges and perspectives of synthesizing MXene QDs are proposed. We hope this review will enlighten researchers to the fabrication of more advancing and promising MXene-based QDs with proprietary properties in diverse applications.

Metal Organic Framework Glasses: A New Platform for Electrocatalysis?

Metal organic framework (MOF) glasses are a coordination network of metal nodes and organic ligands as an undercooled frozen-in liquid, and have therefore broadened the potential of MOF materials in the fundamental research and application scenarios. On the road to deploying MOF glasses as electrocatalysts, it remains several basic scientific hurdles although MOF glasses not only inherit the structural merits of MOFs but also endow with active catalytic features including concentrated defects, metal centers and disorder structure etc. The research on the ionic conductivity, catalytic stability and reactivity of MOF glasses has yielded scientific insights towards its electrocatalytic applications. Here, we first comb the history, definition and basic properties of MOF glasses. Then, we identify the main synthetic methods and characterization techniques. Finally, we advance the potentials and challenges of MOF glasses as electrocatalysts in furthering the understanding of these themes.

Scalable Assembly of High-Quality Graphene Films via Electrostatic-Repulsion Aligning.

Assembling pristine graphene into freestanding films featuring high electrical conductivity, superior flexibility, and robust mechanical strength aims at meeting the all-around high criteria of new-generation electronics. However, voids and defects produced in the macroscopic assembly process of graphene nanosheets severely degrade the performance of graphene films, and mechanical brittleness often limits their applications in wide scenarios. To address such challenges, an electrostatic-repulsion aligning strategy is demonstrated to produce highly conductive, ultraflexible, and multifunctional graphene films. Typically, the high electronegativity of titania nanosheets (TiNS) induces the aligning of negatively charged graphene nanosheets via electrostatic repulsion in the film assembly. The resultant graphene films show fine microstructure, enhanced mechanical properties, and improved electrical conductivity up to 1.285 × 105 S m-1 . Moreover, the graphene films can withstand 5000 repeated folding without structural damage and electrical resistance fluctuation. These comprehensive improved properties, combined with the facile synthesis method and scalable production, make these graphene films a promising platform for electromagnetic interference (EMI) shielding and thermal-management applications in smart and wearable electronics.

Bridging sheet size controls densification of MXene films for robust electromagnetic interference shielding.

Numerous voids among the incompact layer-structure of MXene films result in their low ambient stability and poor innate conductivity for electromagnetic interference (EMI) shielding. Herein, we report a bridging-sheet-size-controlled densification process of MXene films by applying graphene oxide (GO) as a bridging agent. Specifically, the sheet size of GO is tailored to quantify a negative correlation of sheet size with densification for directing the preparation of most compact MXene-GO films. Benefiting from the shortest electron-transport-distance in the most compact structure, the conductivity of the MXene-GO film achieves 1.7 times (∼1.6 × 105 S/m) that of MXene film. The EMI shielding performance (5.2 × 106 dB/m) reaches the record-value among reported MXene films at 10 µm-scale thickness. Moreover, the compact structure boosts the ambient stability of MXene-GO films where the conductivity and EMI shielding performance remain 88.7% and 90.0% after 15 days, respectively. The findings rationale the structure-activity relationship of compact MXene films for flexible electronics.

Localizing Tungsten Single Atoms around Tungsten Nitride Nanoparticles for Efficient Oxygen Reduction Electrocatalysis in Metal-Air Batteries.

Combining isolated atomic active sites with those in nanoparticles for synergizing complex multistep catalysis is being actively pursued in the design of new electrocatalyst systems. However, these novel systems have been rarely studied due to the challenges with synthesis and analysis. Herein, a synergistically catalytic performance is demonstrated with a 0.89 V (vs reversible hydrogen electrode) onset potential in the four-step oxygen reduction reaction (ORR) by localizing tungsten single atoms around tungsten nitride nanoparticles confined into nitrogen-doped carbon (W SAs/WNNC). Through density functional theory calculations, it is shown that each of the active centers in the synergistic entity feature a specific potential-determining step in their respective reaction pathway that can be merged to optimize the intermediate steps involving scaling relations on individual active centers. Impressively, the W SAs/WNNC as the air cathode in all-solid-state Zn-air and Al-air batteries demonstrate competitive durability and reversibility, despite the acknowledged low activity of W-based catalyst toward the ORR.

Ultrafast Macroscopic Assembly of High-Strength Graphene Oxide Membranes by Implanting an Interlaminar Superhydrophilic Aisle.

A macroscopic-assembled graphene oxide (GO) membrane with sustainable high strength presents a bright future for its applications in ionic and molecular filtration for water purification or fast force response for sensors. Traditionally, the bottom-up macroscopic assembly of GO sheets is optimized by widening the interlaminar space for expediting water passage, frequently leading to a compromise in strength, assembly time, and ensemble thickness. Herein, we rationalize this strategy by implanting a superhydrophilic bridge of cobalt-based metal-organic framework nanosheets (NMOF-Co) as an additional water "aisle" into the interlaminar space of GO sheets (GO/NMOF-Co), resulting in a high-strength macroscopic membrane ensemble with tunable thickness from the nanometer scale to the centimeter scale. The GO/NMOF-Co membrane assembly time is only 18 s, 30800 times faster than that of pure GO (154 h). More importantly, the obtained membrane attains a strength of 124.4 MPa, which is more than 3 times higher than that of the GO membrane prepared through filtration. The effect of hydrophilicity on membrane assembly is also investigated by introducing different intercalants, suggesting that, except for the interlamellar spacing, the interlayered hydrophilicity plays a more decisive role in the macroscopic assembly of GO membranes. Our results give a fundamental implication for fast macroscopic assembly of high-strength 2D materials.

A chainmail effect of ultrathin N-doped carbon shell on Ni2P nanorod arrays for efficient hydrogen evolution reaction catalysis.

Exploring innovation strategies has huge potential to significantly improving both activity and stability of current catalysts. Here, a chainmail design is proposed to enable the electronic interaction of ultrathin nitrogen-doped carbon shell with Ni2P nanorod core arrayed on nickel foam (Ni2P@NC/NF) for simultaneously promoting the activity and stability in both alkaline and neutral hydrogen evolution reaction (HER). The easy penetration of valence electrons from active Ni2P core to NC shell enables the obvious improvement of HER performance compared to pure Ni2P. In 1 M KOH and 1 M PBS solution, the resultant Ni2P@NC/NF requires the ultralow overpotentials of only 93 and 96 mV to drive the current density of 10 mA cm-2 with the Faradaic efficiency of 96% and 94%, respectively. Remarkably, such a chainmail design also reveals an obviously improved stability with almost negligible performance degradation under the current density of 20 mA cm-2 for 30 h. Theoretical calculations confirm that the nitrogen-doped carbon shell improves the durability of transition metal phosphides by increasing the dissolution resistance of Ni atoms. The proposed concept may create a new pathway for synchronizing high activity and robust stability in manipulating heterogeneous catalytic properties.

Quench-Induced Surface Engineering Boosts Alkaline Freshwater and Seawater Oxygen Evolution Reaction of Porous NiCo2 O4 Nanowires.

The electrochemical oxygen evolution reaction (OER) by efficient catalysts is a crucial step for the conversion of renewable energy into hydrogen fuel, in which surface/near-surface engineering has been recognized as an effective strategy for enhancing the intrinsic activities of the OER electrocatalysts. Herein, a facile quenching approach is demonstrated that can simultaneously enable the required surface metal doping and vacancy generation in reconfiguring the desired surface of the NiCo2 O4 catalyst, giving rise to greatly enhanced OER activities in both alkaline freshwater and seawater electrolytes. As a result, the quenched-engineered NiCo2 O4 nanowire electrode achieves a current density of 10 mA cm-2 at a low overpotential of 258 mV in 1 m KOH electrolyte, showing the remarkable catalytic performance towards OER. More impressively, the same electrode also displays extraordinary activity in an alkaline seawater environment and only needs 293 mV to reach 10 mA cm-2 . Density functional theory (DFT) calculations reveal the strong electronic synergies among the metal cations in the quench-derived catalyst, where the metal doping regulates the electronic structure, thereby yielding near-optimal adsorption energies for OER intermediates and giving rise to superior activity. This study provides a new quenching method to obtain high-performance transition metal oxide catalysts for freshwater/seawater electrocatalysis.

Dispersed FeOx nanoparticles decorated with Co2SiO4 hollow spheres for enhanced oxygen evolution reaction.

Oxygen evolution reaction (OER) has drawn ever-increasing attention because of its essential role in various renewable-energy technologies. In spite of tremendous research efforts, developing high-performance OER catalysts at low cost remains a great challenge. Inspired by two earth-abundant elements Fe and Si, herein, we report a Fe-Co2SiO4 composite consisting of well dispersed iron oxide (FeOx) decorated Co2SiO4 hollow nanospheres as an economical and promising OER catalyst. Although Co2SiO4 or FeOx alone has little OER activity, their composite exhibits satisfied performance, that is highly related to geometric effect and bimetal component electronic interactions. The Fe-Co2SiO4 composite exhibits comparable catalytic activity to most of transition mental oxide/hydroxide relevant composites at 10 mA cm-2. It is even 1.6 times higher than commercial RuO2 electrocatalyst at high current density 100 mA cm-2 in alkaline solution. In this work, surface decoration of transition metal silicate provides a new horizon to design high-performance and economical OER catalysts.

Manipulating Interfaces of Electrocatalysts Down to Atomic Scales: Fundamentals, Strategies, and Electrocatalytic Applications.

Raising electrocatalysis by rationally devising catalysts plays a core role in almost all renewable energy conversion and storage systems. The principal catalytic properties can be controlled and improved well by manipulation of interfaces, ascribed to the interactions among different components/players at the interfaces. In particular, manipulating interfaces down to atomic scales is becoming increasingly attractive, not only because those atoms at around the interface are the key players during electrocatalysis, but also, understandings on the atomic level electrocatalysis allow one to gain deep insights into the reaction mechanism. With the feature down-sizing to atomic scales, there is a timely need to redefine the interfaces, as some of them have gone beyond the conventionally perceived interfacial concept. In this overview, the key active players participating in the interfacial manipulation of electrocatalysts are examined, from a new angle of "atomic interface," including those individual atoms, defects, and their interactions, together with the essential characterization techniques for them. The specific approaches and pathways to engineer better atomic interfaces are investigated, and thus to enable the unique electrocatalysis for targeted applications. Looking beyond recent progress, the challenges and prospects of the atomic level interfacial engineering are also briefly visited.

Electrospun One-Dimensional Electrocatalysts for Oxygen Reduction Reaction: Insights into Structure-Activity Relationship.

Oxygen reduction reaction (ORR) is an efficiency-determining process at the cathode in several energy storage and conversion devices, typically such as metal-air batteries and fuel cells. To date, a considerable amount of ORR electrocatalysts have been purposely exploited to address the key issues of high overpotentials and sluggish electrochemical kinetics. Electrospinning is a popular additive manufacturing technology, enabling the production of one-dimensional (1D) electrocatalysts with outstanding chemical stability and structural diversity. However, compared with the well-studied composite/structural design as well as performance advancement, insights into structure-activity relationship are yet to be settled. To clarify this key issue, herein, a dedicated review on the structure-activity relationship between the 1D architectures of electrospun electrocatalysts and their catalytic ORR property is presented. First, the development and principles of electrospinning technique, the composition regulation- and structure design-oriented fundamentals are summarized by imputing the perspectives of mechanistic understanding. Then, the typical examples of nanofiber-shaped and nanofiber-supported electrocatalysts with different compositions and structures for ORR are implemented to establish different structure-activity relationship by comparative studies. Finally, we also identify some ongoing challenges and present future perspectives to direct the precise manipulation of structure-activity relationship for further activation and optimization of electrospun 1D electrocatalysts.

Black Phosphorus@Ti3C2Tx MXene Composites with Engineered Chemical Bonds for Commercial-Level Capacitive Energy Storage.

Electrolyte-accessibly porous yet densely packed MXene composite electrodes with high ion-accessible surface and rapid ion transport rate have shown exceptional promise for high-volumetric-performance supercapacitors (SCs), but they are largely limited by the insufficient rate capability and poor electrochemical cyclability, in association with the instability in mechanical robustness of the porous network structures. Taking advantage of chemical bonding design, herein a black phosphorus (BP)@MXene compact film of 3D porous network structure is successfully made by in situ growth of BP nanoparticles on crumbled MXene flakes. The strong interfacial interaction (Ti-O-P bonds) formed at the BP-MXene interfaces not only enhances the atomic charge polarization in the BP-MXene heterostructures, leading to efficient interfacial electron transport, but also stabilizes the 3D porous yet dense architecture with much improved mechanical robustness. Consequently, fully packaged SCs using the BP@MXene composite films with a practical-level of mass loading (∼15 mg cm-2) deliver a high stack volumetric energy density of 72.6 Wh L-1, approaching those of lead-acid batteries (50-90 Wh L-1), together with a long-term stability (90.58% capacitance retention after 50000 cycles). The achievement of such high energy density bridges the gap between traditional batteries and SCs and represents a timely breakthrough in designing compact electrodes toward commercial-level capacitive energy storage.

Quasi-Paired Pt Atomic Sites on Mo2 C Promoting Selective Four-Electron Oxygen Reduction.

Atomically dispersed Pt species are advocated as a promising electrocatalyst for the oxygen reduction reaction (ORR) to boost noble metal utilization efficiency. However, when assembled on various substrates, isolated Pt single atoms are often demonstrated to proceed through the two-electron ORR pathway due to the unfavorable O─O bond cleavage thermodynamics in the absence of catalytic ensemble sites. In addition, although their distinct local coordination environments at the exact single active sites are intensively explored, the interactions and synergy between closely neighboring single atom sites remain elusive. Herein, atomically dispersed Pt monomers strongly interacting on a Mo2 C support is demonstrated as a model catalyst in the four-electron ORR, and the beneficial interactions between two closely neighboring and yet non-contiguous Pt single atom sites (named as quasi-paired Pt single atoms) are shown. Compared to isolated Pt single atom sites, the quasi-paired Pt single atoms deliver a superior mass activity of 0.224 A mg-1 Pt and near-100% selectivity toward four-electron ORR due to the synergistic interaction from the two quasi-paired Pt atom sites in modulating the binding mode of reaction intermediates. Our first-principles calculations reveal a unique mechanism of such quasi-paired configuration for promoting four-electron ORR.

Electrocatalytically inactive copper improves the water adsorption/dissociation on Ni3S2 for accelerated alkaline and neutral hydrogen evolution.

Nickel dichalcogenides, especially Ni3S2, present inferior alkaline and neutral hydrogen evolution activity due to their sluggish water dissociation kinetics. Although these materials hold promise as non-noble metal-based electrocatalysts for the hydrogen evolution reaction (HER) in acidic media, developing efficient strategies to enhance the water dissociation processes of nickel dichalcogenides in alkaline and neutral solutions is also an important area of research. The present work discloses an electrocatalytically inactive copper doping strategy to promote the water adsorption and dissociation process of Ni3S2 (Cu-Ni3S2) nanoparticles supported on nickel foam (NF) towards improving the alkaline and neutral hydrogen evolution reactions. Based on combined density functional theory calculations and electrochemical characterizations, the doping of Cu can accelerate the Volmer step and therefore strengthen the water adsorption/dissociation on the respective Ni sites and S sites during the HER process. As a result, the electrocatalyst exhibits superior and stable HER performance in both 1 M KOH and 1 M phosphate-buffered saline (PBS) solutions, with much lower overpotentials of 121 and 228 mV at a current density of 10 mA cm-2, respectively, in comparison to bare Ni3S2. We therefore conclude that the tailored control of the water adsorption/dissociation capability of Ni3S2 will open significant opportunities for the rational design of alkaline and neutral electrocatalysts from earth-abundant and stable materials.

Fiber-in-tube and particle-in-tube hierarchical nanostructures enable high energy density of MnO2-based asymmetric supercapacitors.

Manganese dioxide (MnO2) promises for high-performance asymmetric suprecapacitors, owing to its high theoretical capacity, abundant source, and low cost. However, insufficient practically-achievable capacity and relatively narrow voltage window in alkaline electrolyte are blocking high energy density of MnO2-based supercapacitors, where strategies for activating its capacitive performance and widening voltage window are the top priorities to solve the bottleneck problems. Herein, both the fiber-in-tube (NCCM-FiT) and particle-in-tube (NCCM-PiT) nanostructures coulping active NiCoOx nanoparticles and conductive carbon with MnO2 tubes have been purposely fabricated, using the electrospun nickel cobalt oxides/carbon nanofibers (NCO/CNFs) as the self-template agents for enhanced energy density of MnO2-based supercapacitors. These hierarchical hollow nanotubes with gradient pores and unique compositions yield excellent capacitive properties, in terms of a competitive capacity (431.7 F g-1 or 431.7 C g-1, 0.5 A g-1), which is 2.7 times that of the MnO2 nanotubes-based electrodes. A maximum energy density of 46.4 Wh kg-1 is obtained at the power density of 400 W kg-1 for the asymmetric device assembled with the NCCM-PiT-based positive electrode and the electrospun CNFs-based negative electrode. The remarkable energy density demonstrated by these hierarchical hollow nanotubes exemplifies a novel and effective design in electrode materials for the asymmetric supercapacitors (ASCs) with superior performance.

Efficient Hydrogen Evolution of Oxidized Ni-N3 Defective Sites for Alkaline Freshwater and Seawater Electrolysis.

For mass production of high-purity hydrogen fuel by electrochemical water splitting, seawater electrolysis is an attractive alternative to the traditional freshwater electrolysis due to the abundance and low cost of seawater in nature. However, the undesirable chlorine ion oxidation reactions occurring simultaneously with seawater electrolysis greatly hinder the overall performance of seawater electrolysis. To tackle this problem, electrocatalysts of high activity and selectivity with purposely modulated coordination and an alkaline environment are urgently required. Herein, it is demonstrated that atomically dispersed Ni with triple nitrogen coordination (Ni-N3 ) can achieve efficient hydrogen evolution reaction (HER) performance in alkaline media. The atomically dispersed Ni electrocatalysts exhibit overpotentials as low as 102 and 139 mV at 10 mA cm-2 in alkaline freshwater and seawater electrolytes, respectively, which compare favorably with those previously reported. They also deliver large current densities beyond 200 mA cm-2 at lower overpotentials than Pt/C, as well as show negligible current attenuation over 14 h. The X-ray absorption fine structure (XAFS) experimental analysis and density functional theory (DFT) calculations verify that the Ni-N3 coordination, which exhibits a lower coordination number than Ni-N4 , facilitates water dissociation and hydrogen adsorption, and hence enhances the HER activity.