Remodeling the Electronic Structure of Metallic Nickel and Ruthenium via Alloying in a Molecular Template for Sustainable Hydrogen Evolution.

The reasonably constructed high-performance electrocatalyst is crucial to achieve sustainable electrocatalytic water splitting. Alloying is a prospective approach to effectively boost the activity of metal electrocatalysts. However, it is a difficult subject for the controllable synthesis of small alloying nanostructures with high dispersion and robustness, preventing further application of alloy catalysts. Herein, we propose a well-defined molecular template to fabricate a highly dispersed NiRu alloy with ultrasmall size. The catalyst presents superior alkaline hydrogen evolution reaction (HER) performance featuring an overpotential as low as 20.6 ± 0.9 mV at 10 mA·cm-2. Particularly, it can work steadily for long periods of time at industrial-grade current densities of 0.5 and 1.0 A·cm-2 merely demanding low overpotentials of 65.7 ± 2.1 and 127.3 ± 4.3 mV, respectively. Spectral experiments and theoretical calculations revealed that alloying can change the d-band center of both Ni and Ru by remodeling the electron distribution and then optimizing the adsorption of intermediates to decrease the water dissociation energy barrier. Our research not only demonstrates the tremendous potential of molecular templates in architecting highly active ultrafine nanoalloy but also deepens the understanding of water electrolysis mechanism on alloy catalysts.

A confinement-regulated (H3C-NH3)+ ion as a smallest dual-wheel rotator showing bisected rotation dynamics.

On the basis of variable-temperature single-crystal X-ray diffraction, rotational energy barrier analysis, variable-temperature/frequency dielectric response, and molecular dynamics simulations, here we report a new crystalline supramolecular rotor (CH3NH3)(18-crown-6)[CuCl3], in which the (H3C-NH3)+ ion functions as a smallest dual-wheel rotator showing bisected rotation dynamics, while the host 18-crown-6 macrocycle behaves as a stator that is not strictly stationary. This study also provides a helpful insight into the dynamics of ubiquitous -CH3/-NH3 groups confined in organic or organic-inorganic hybrid solids.

Molecular rotators anchored on a rod-like anionic coordination polymer adhered by charge-assisted hydrogen bonds.

On the basis of variable-temperature single-crystal X-ray diffraction, variable-temperature/frequency dielectric analysis, variable-temperature solid-state nuclear magnetic resonance spectroscopy, and molecular dynamics simulations, here we present a new model of crystalline supramolecular rotor (i-PrNHMe2)[CdBr3], where a conformationally flexible near-spherical (i-PrNHMe2)+ cation functions as a rotator and a rod-like anionic coordination polymer {[CdBr3]-}∞ acts as the stator, and the adhesion of them is realized by charge-assisted hydrogen bonds.

Optimizing the Spatial Density of Single Co Sites via Molecular Spacing for Facilitating Sustainable Water Oxidation.

Advances in single-atom (-site) catalysts (SACs) provide a new solution of atomic economy and accuracy for designing efficient electrocatalysts. In addition to a precise local coordination environment, controllable spatial active structure and tolerance under harsh operating conditions remain great challenges in the development of SACs. Here, we show a series of molecule-spaced SACs (msSACs) using different acid anhydrides to regulate the spatial density of discrete metal phthalocyanines with single Co sites, which significantly improve the effective active-site numbers and mass transfer, enabling one of the msSACs connected by pyromellitic dianhydride to exhibit an outstanding mass activity of (1.63 ± 0.01) × 105 A·g-1 and TOFbulk of 27.66 ± 1.59 s-1 at 1.58 V (vs RHE) and long-term durability at an ultrahigh current density of 2.0 A·cm-2 under industrial conditions for oxygen evolution reaction. This study demonstrates that the accessible spatial density of single atom sites can be another important parameter to enhance the overall performance of catalysts.

Temperature-Tuned Variable Confined Space for Modulating Dipolar Polarization of a Disc-Shaped Ammonium Ion.

Free accessible confined space and loose interaction are crucial for most solid-state ionic motions. Here, by using a near-spherical anion and a disc-shaped ammonium as two distinct but rigid building blocks, we report a new ionic crystal, (HMIm)3[La(NO3)6] (HMIm = 1-methyl-1H-imidazol-3-ium), in which the different confined spaces of three (HMIm)+ ions are fine-tuned over a broad temperature range. This effect can be utilized to modulate the dipolar polarization across a wide temperature/frequency range. Additionally, small-scale substitution of (HMIm)+ by its isomer of almost identical shape/size affords molecular solid solutions, which can further tune the dipolar polarization by varying the doping ratio. It is revealed that the differences in dipole moment and hydrogen bond rather than that of shape/size lead to a distorted crystalline environment for these solid solutions. Overall, we provide an exceptional model for understanding and regulating the dipole motion of polar aromatic molecules/ions in a crystalline environment.

Biomass-Derived Carbon-Based Multicomponent Integration Catalysts for Electrochemical Water Splitting.

Electrocatalytic water splitting powered by sustainable electricity is a crucial approach for the development of new generation green hydrogen technology. Biomass materials are abundant and renewable, and the application of catalysis can increase the value of some biomass waste and turn waste into fortune. Converting economical and resource-rich biomass into carbon-based multicomponent integrated catalysts (MICs) has been considered as one of the most promising ways to obtain inexpensive, renewable and sustainable electrocatalysts in recent years. In this review, recent advances in biomass-derived carbon-based MICs towards electrocatalytic water splitting are summarized, and the existing issues and key aspects in the development of these electrocatalysts are also discussed and prospected. The application of biomass-derived carbon-based materials will bring some new opportunities in the fields of energy, environment, and catalysis, as well as promote the commercialization of new nanocatalysts in the near future.

Atomically Dispersed Dual-Metal Sites Showing Unique Reactivity and Dynamism for Electrocatalysis.

The real structure and in situ evolution of catalysts under working conditions are of paramount importance, especially for bifunctional electrocatalysis. Here, we report asymmetric structural evolution and dynamic hydrogen-bonding promotion mechanism of an atomically dispersed electrocatalyst. Pyrolysis of Co/Ni-doped MAF-4/ZIF-8 yielded nitrogen-doped porous carbons functionalized by atomically dispersed Co-Ni dual-metal sites with an unprecedented N8V4 structure, which can serve as an efficient bifunctional electrocatalyst for overall water splitting. More importantly, the electrocatalyst showed remarkable activation behavior due to the in situ oxidation of the carbon substrate to form C-OH groups. Density functional theory calculations suggested that the flexible C-OH groups can form reversible hydrogen bonds with the oxygen evolution reaction intermediates, giving a bridge between elementary reactions to break the conventional scaling relationship.

Self-Supporting Co/CeO2 Heterostructures for Ampere-Level Current Density Alkaline Water Electrolysis.

Remodeling the active surface through fabricating heterostructures can substantially enhance alkaline water electrolysis driven by renewable electrical energy. However, there are still great challenges in the synthesis of highly reactive and robust heterostructures to achieve both ampere-level current density hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). Herein, we report a new Co/CeO2 heterojunction self-supported electrode for sustainable overall water splitting. The self-supporting Co/CeO2 heterostructures required only low overpotentials of 31.9 ± 2.2, 253.3 ± 2.7, and 316.7 ± 3 mV for HER and 214.1 ± 1.4, 362.3 ± 1.9, and 400.3 ± 3.7 mV for OER at 0.01, 0.5, and 1.0 A·cm-2, respectively, being one of the best Co-based bifunctional electrodes. Electrolyzer constructed from this electrode acting as an anode and cathode merely required cell voltages of 1.92 ± 0.02 V at 1.0 A·cm-2 for overall water splitting. Multiple characterization techniques combined with density functional theory calculations disclosed the different active sites on the anode and cathode, and the charge redistributions on the heterointerfaces that can optimize the adsorption of H and oxygen-containing intermediates, respectively. This study presents the tremendous prospective of self-supporting heterostructures for effective and economical overall water splitting.

Molecule-Enhanced Electrocatalysis of Sustainable Oxygen Evolution Using Organoselenium Functionalized Metal-Organic Nanosheets.

Remolding the reactivity of metal active sites is critical to facilitate renewable electricity-powered water electrolysis. Doping heteroatoms, such as Se, into a metal crystal lattice has been considered an effective approach, yet usually suffers from loss of functional heteroatoms during harsh electrocatalytic conditions, thus leading to the gradual inactivation of the catalysts. Here, we report a new heteroatom-containing molecule-enhanced strategy toward sustainable oxygen evolution improvement. An organoselenium ligand, bis(3,5-dimethyl-1H-pyrazol-4-yl)selenide containing robust C-Se-C covalent bonds equipped in the precatalyst of ultrathin metal-organic nanosheets Co-SeMON, is revealed to significantly enhance the catalytic mass activity of the cobalt site by 25 times, as well as extend the catalyst operation time in alkaline conditions by 1 or 2 orders of magnitude compared with these reported metal selenides. A combination of various in situ/ex situ spectroscopic techniques, ab initio molecular dynamics, and density functional theory calculations unveiled the organoselenium intensified mechanism, in which the nonclassical bonding of Se to O-containing intermediates endows adsorption-energy regulation beyond the conventional scaling relationship. Our results showcase the great potential of molecule-enhanced catalysts for highly efficient and economical water oxidation.

Highly selective generation of singlet oxygen from dioxygen with atomically dispersed catalysts.

Singlet oxygen (1O2) as an excited electronic state of O2 plays a significant role in ubiquitous oxidative processes from enzymatic oxidative metabolism to industrial catalytic oxidation. Generally, 1O2 can be produced through thermal reactions or the photosensitization process; however, highly selective generation of 1O2 from O2 without photosensitization has never been reported. Here, we find that single-atom catalysts (SACs) with atomically dispersed MN4 sites on hollow N-doped carbon (M1/HNC SACs, M = Fe, Co, Cu, Ni) can selectively activate O2 into 1O2 without photosensitization, of which the Fe1/HNC SAC shows an ultrahigh single-site kinetic value of 3.30 × 1010 min-1 mol-1, representing top-level catalytic activity among known catalysts. Theoretical calculations suggest that different charge transfer from MN4 sites to chemisorbed O2 leads to the spin-flip process and spin reduction of O2 with different degrees. The superior capacity for highly selective 1O2 generation enables the Fe1/HNC SAC as an efficient non-radiative therapeutic agent for in vivo inhibition of tumor cell proliferation.

Platinum-Ruthenium Single Atom Alloy as a Bifunctional Electrocatalyst toward Methanol and Hydrogen Oxidation Reactions.

The precise regulation for the structural properties of nanomaterials at the atomic scale is an effective strategy to develop high-performance catalysts. Herein, a facile dual-regulation approach was developed to successfully synthesize Ru1Ptn single atom alloy (SAA) with atomic Ru dispersed in Pt nanocrystals. High-angle annular dark-field scanning transmission electron microscopy and X-ray absorption fine structure demonstrated that Ru atoms were dispersed in Pt nanocrystals as single atoms. Impressively, the Ru1Ptn-SAA exhibited an ultrahigh specific activity (23.59 mA cm-2) and mass activity (2.805 mA/µg-PtRu) for methanol oxidation reaction (MOR) and exhibited excellent exchange current density activity (1.992 mA cm-2) and mass activity (4.71 mA/µg-PtRu) for hydrogen oxidation reaction (HOR). Density functional theory calculations revealed that the introduction of Ru atoms greatly reduced the reaction free energy for the decomposition of water molecules, which promoted the removal of CO* in the MOR process and adjusted the Gibbs free energy of hydrogen and hydroxyl adsorption to promote the HOR. Our work provided an effective idea for the development of high performance electrocatalysts.

Insights into the Molecular Dynamics of Quasi-Spherical (Chloromethyl)triethylammonium Confined in a Weakly Bound Ionic Cocrystal.

Here, we report a weakly bound ionic cocrystal, (Et3NCH2Cl)2[ZnCl4], which undergoes a reversible structural phase transition owing to the switched molecular dynamics of the quasi-spherical (Et3NCH2Cl)+ cation from static to dynamic. Interestingly, a unique rolling and moving mechanism is uncovered for such a cation in the high-temperature phase, where its two methylene groups exhibit different kinetic energy barriers. This study provides a meaningful insight into the solid-state molecular dynamics of large-size quasi-spherical molecules that contain both a rigid core and flexible shell.

Confinement synthesis in porous molecule-based materials: a new opportunity for ultrafine nanostructures.

A balance between activity and stability is greatly challenging in designing efficient metal nanoparticles (MNPs) for heterogeneous catalysis. Generally, reducing the size of MNPs to the atomic scale can provide high atom utilization, abundant active sites, and special electronic/band structures, for vastly enhancing their catalytic activity. Nevertheless, due to the dramatically increased surface free energy, such ultrafine nanostructures often suffer from severe aggregation and/or structural degradation during synthesis and catalysis, greatly weakening their reactivities, selectivities and stabilities. Porous molecule-based materials (PMMs), mainly including metal-organic frameworks (MOFs), covalent organic frameworks (COFs) and porous organic polymers (POPs) or cages (POCs), exhibit high specific surface areas, high porosity, and tunable molecular confined space, being promising carriers or precursors to construct ultrafine nanostructures. The confinement effects of their nano/sub-nanopores or specific binding sites can not only effectively limit the agglomeration and growth of MNPs during reduction or pyrolysis processes, but also stabilize the resultant ultrafine nanostructures and modulate their electronic structures and stereochemistry in catalysis. In this review, we highlight the latest advancements in the confinement synthesis in PMMs for constructing atomic-scale nanostructures, such as ultrafine MNPs, nanoclusters, and single atoms. Firstly, we illustrated the typical confinement methods for synthesis. Secondly, we discussed different confinement strategies, including PMM-confinement strategy and PMM-confinement pyrolysis strategy, for synthesizing ultrafine nanostructures. Finally, we put forward the challenges and new opportunities for further applications of confinement synthesis in PMMs.

Silver(I)-Based Molecular Perovskite Energetic Compounds with Exceptional Thermal Stability and Energetic Performance.

In recent years, molecular perovskite energetic materials have attracted more attention because of their simple synthesis processes, high thermal stabilities, excellent performances, and great significance as a design platform for energetic materials. To explore the possibility of the application of molecular perovskite energetic materials in heat-resistant explosives, four silver(I)-based molecular perovskite energetic compounds, (H2A)[Ag(ClO4)3], where H2A = piperazine-1,4-diium (H2pz2+) for PAP-5, 1-methyl-piperazine-1,4-diium (H2mpz2+) for PAP-M5, homopiperazine-1,4-diium (H2hpz2+) for PAP-H5, and 1,4-diazabicyclo[2.2.2]octane-1,4-diium (H2dabco2+) for DAP-5, were synthesized by a one-pot self-assembly strategy and structurally characterized. The single-crystal structures indicated that PAP-5, PAP-M5, and DAP-5 possess cubic perovskite structures while PAP-H5 possesses a hexagonal perovskite structure. Differential thermal analyses showed that their onset decomposition temperatures are >308.3 °C. For PAP-5 and DAP-5, they have not only exceptional calculated detonation parameters (D values of 8.961 and 8.534 km s-1 and P values of 42.4 and 37.9 GPa, respectively) but also the proper mechanical sensitivity (impact sensitivities of ≤10 J for PAP-5 and 3 J for DAP-5 and friction sensitivities of ≤5N for both PAP-5 and DAP-5) and thus are of interest as potential heat-resistant primary explosive components.

Interpolation between W Dopant and Co Vacancy in CoOOH for Enhanced Oxygen Evolution Catalysis.

Electronic structure engineering via integrating two defect structures with opposite modulation effects holds the key to fully unlocking the power of a catalyst. Herein, an interpolation principle is proposed to activate CoOOH via W doping and Co vacancies for the oxygen evolution reaction. Density functional theory suggests opposite roles for the W dopant and the Co vacancy but a synergy between them in tuning the electronic states of the Co site, leading to near-ideal intermediate energetics and dramatically lowered catalytic overpotential. Experimental studies confirm the modulation of the electronic structure and validate the greatly enhanced catalytic activity with a small overpotential of 298.5 mV to drive 50 mA cm-2 . The discovery of the interpolation between dopants and vacancies opens up a new methodology to design efficient catalysts for various electrochemical reactions.

A single-atom Cu-N2 catalyst eliminates oxygen interference for electrochemical sensing of hydrogen peroxide in a living animal brain.

Hydrogen peroxide (H2O2) plays essential roles in various physiological and pathological processes. The electrochemical hydrogen peroxide reduction reaction (HPRR) has been recognized as an efficient approach to H2O2 sensing; however, the HPRR has always suffered from low tolerance against the oxygen reduction reaction (ORR), resulting in poor selectivity of the HPRR-based sensing platform. In this study, we find that the electrochemical HPRR occurs preferentially compared to the ORR when isolated Cu atoms anchored on carbon nitride (Cu1/C3N4) are used as a single-atom electrocatalyst, which is theoretically attributed to the lower energy barrier of the HPRR than that of the ORR on a Cu1/C3N4 single-atom catalyst (SAC). With the Cu1/C3N4 SAC as the electrocatalyst, we fabricated microsensors that have a good response to H2O2, but not to O2 or other electroactive neurochemicals. When implanted into a living rat brain, the microsensor shows excellent in vivo sensing performance, enabling its application in real-time quantitative investigation of the dynamics of H2O2 production induced by mercaptosuccinate and glutathione monoethyl ester in a living animal brain.

Solid solutions of flexible host-guest supramolecules for tuning molecular motion and phase transitions.

By utilizing a supramolecular complex rather than an individual molecule as a deformable and elastic substitutional component, we put forward a solid-solution strategy and demonstrate an example of how two related yet non-isostructural crystalline host-guest compounds can form molecular solid solutions. Interestingly, such a strategy can effectively and continuously modulate the molecular motion and phase transition in them, as revealed by the variable-temperature/frequency dielectric responses.

Octanuclear Cobalt(II) Cluster-Based Metal-Organic Framework with Caged Structure Exhibiting the Selective Adsorption of Ethane over Ethylene.

A novel metal-organic framework (MOF) of [Co8(OH)4(TCA)4(H2O)4]n (abbreviation: JXNU-9) based on the unique octanuclear Co8(µ3-OH)4 clusters linked by 4,4',4″-nitrilotribenzoate (TCA3-) ligands featuring small caged structures and one-dimensional channels was prepared and characterized. JXNU-9 shows a high C2H6 uptake capacity of 3.60 mmol g-1 (4.46 mmol cm-3) at 298 K and 1 atm with a small isosteric heat of adsorption (23.6 kJ mol-1) and a moderate C2H6/C2H4 adsorption selectivity of 1.7, resulting in excellent C2H6/C2H4 separation performance. The pore walls decorated by plenty of aromatic rings provide π-electron-cloud-surrounding environments to accommodate the large polarizable C2H6 molecules. The calculations demonstrate that the rich π-systems in JXNU-9 facilitate an adsorption affinity for large C2H6 molecules through multiple C-H···π interactions. Additionally, the open metal sites located in the concave pores with a close Co···Co separation (4.21 Å) in octanuclear Co8(µ3-OH)4 clusters make the open metal sites inaccessible for the C2H4 molecule with a kinetic diameter of 4.163 Å. Thus, the annihilation of open metal sites in this structure is achieved, which further facilitates the C2H6-selective C2H6/C2H4 separation.

Graphene-Like Hydrogen-Bonded Melamine-Cyanuric Acid Supramolecular Nanosheets as Pseudo-Porous Catalyst Support.

Behaving as structural protectors and electronic modulators, catalyst supports such as graphene derivatives are generally constructed by covalent bonds. Here, hydrogen-bonded ultrathin nanosheets are reported as a new type of catalyst support. Melamine (M) and cyanuric acid (CA) molecules self-assemble to form the graphite-like hydrogen-bonded co-crystal M-CA, which can be easily exfoliated by ultrasonic treatment to yield ultrathin nanosheets with thickness of ≈1.6 nm and high stability at pH = 0. The dynamic nanosheets form adaptive defects/pores in the synthetic process of CoP nanoparticles, giving embedded composite with high hydrogen evolution activity (overpotential of 66 mV at 10 mA cm-2 ) and stability. Computational calculations, X-ray photoelectron spectroscopy, and X-ray absorption spectroscopy unveil the electron modulation effects of the nanosheets. This pseudo-porous catalyst support also can be applied to other metal phosphides.

Electrochemically Controlled Synthesis of Ultrathin Nickel Hydroxide Nanosheets for Electrocatalytic Oxygen Evolution.

The development of oxygen evolution reaction (OER) catalysts with high activity and high stability through convenient and economical methods is greatly important for the promotion of hydrogen energy based on electrolysis technology. Herein, by using an unconventional high electrodeposition potential, novel petal-like clusters constructed by cross-linking ultrathin nickel hydroxide nanosheets were controllably synthesized on nickel foam (or copper foam or carbon cloth) and the effect of electrodeposition conditions on their OER performance was carefully explored. Due to the abundant catalytically active sites, promoting electron conduction/mass transmission from the specific micro-nano structure, as well as the ultrasmall thickness of ∼3.0 nm, the optimized α-Ni(OH)2/NF self-supporting electrode exhibits excellent electrocatalytic performance for OER, merely requiring low overpotentials of 192 and 240 mV to yield current densities of 10 and 100 mA cm-2 in 1.0 M KOH, respectively, which surpassed those of all of the reported nickel hydroxide/oxides and the benchmark RuO2. Moreover, α-Ni(OH)2/NF can drive the high-current density (500-1000 mA cm-2) OER at low overpotentials, meeting the requirements of potential industrial applications.