Construction of Pd-Te Intermetallic Compounds to Achieve Ultrastable Oxygen Reduction Activity.

Palladium (Pd)-transition metal alloys have the potential to regulate the intermediate surface adsorption strength in oxygen reduction reactions (ORR), making them a promising substitute for platinum-based catalysts. Nonetheless, prolonged electrochemical cycling can lead to the depletion of transition metals, resulting in structural degradation and poor durability. Herein, the synthesis of alloy catalysts (Pd25%Te75%) containing Pd and the metalloid tellurium (Te) through a one-step reduction method is reported. Characterizations of powder X-ray photoelectron spectroscopy, X-ray diffraction, and high-resolution transmission electron microscopy demonstrated both uniform dispersion and strong binding force of elements within the PdTe alloy, along with providing crystallographic details of associated compounds. Based on density functional theory calculations, PdTe had a more negative d-band center than that of pure Pd, which reduces the adsorption capacity between active sites and intermediates in the ORR, and therefore enhances reaction kinetics. The Pd25%Te75% exhibited excellent ORR activity, and its onset and half-wave potentials were ∼0.98 and ∼0.90 V, respectively, at 1600 rpm within the O2-saturated 1.0 M KOH. Significantly, accelerated durability tests achieved exceptional stability, and half-wave potential just decayed by 4 mV after 30000 consecutive cycles. Moreover, this study aims to promote the preparation of Pd and metalloid alloys for other energy conversion applications.

Interfacial oxygen atom modification of a PdSn alloy to boost oxygen reduction in zinc-air batteries.

Modifying the surface of a catalyst with heteroatoms can regulate the interfacial atomic valence state and adjust the charge distribution, which is promising for obtaining desirable platinum carbon catalyst (Pt/C)-matched oxygen reduction reaction (ORR) catalytic performance. Here, we developed an efficient method to access O-rich crystalline interfacial-exposed palladium-tin alloy (111) crystal surfaces [Pd3Sn (111)] for highly efficient ORR via direct reduction of Pd/Sn metal salt species that are well dispersed in a nitrogen, phosphorus-doped carbonaceous (NPC) substrate. In addition to the other materials, preembedded Pd/Sn metal salt species in NPC control the release of metal sources upon reduction in the liquid phase, resulting in the grafting of an as-prepared PdSn alloy with many merits, such as efficient electron conduction, short-range crystallinity and increased crystal interface exposure. The presence of a considerable quantity of oxygen atoms at the interface of small-sized PdSn alloys on NPC substrates has been methodically verified by powder X-ray diffraction, high-resolution transmission electron microscopy and X-ray photoelectron spectroscopy characterizations. The PdSn-O sample exhibited excellent ORR activity, achieving an onset potential of âˆ¼0.99 V and a half-wave potential of âˆ¼0.88 V at 1600 rpm in O2-saturated 1.0 M KOH. Density functional theory simulations of pure Pd, Pd-O, the PdSn alloy and PdSn-O suggest that interfacial oxygen atom modification is responsible for the significantly improved ORR activity. The assembled zinc-air battery provides a high specific power of 218.9 mW cm-2 and a specific capacity of 810.6 mAh gZn-1. Our approach has the potential to stimulate the preparation of O-rich crystalline interfacial-exposed alloy compounds for other energy conversion applications.

Waste to wealth: atomically dispersed cobalt-nitrogen-carbon from spent LiCoO2.

Atomic cobalt-nitrogen-carbon (Co-NC) material was synthesized using spent LiCoO2, and contained a heavy Co-N4 loading (1.42 at%). The synthesized Co-NC exhibited high oxygen reduction reaction activity (with onset and half-wave potentials of 0.97 V and 0.87 V, respectively) and robust Al-air battery performance, delivering a specific power of 121.3 mW cm-2.

N4-Vacancy-Functionalized Carbon for High-Rate Li-Ion Storage.

Although heteroatom doping and pore management separately influence the Li+ adsorption and Li+ diffusion properties, respectively, merging their functions into a single unit is intriguing and has not been fully investigated. Herein, we have successfully incorporated both heteroatom doping and pore management within the same functional unit of N4-vacancy motifs, which is realized via acid etching of formamide-derived Zn-N4-functionalized carbon materials (Zn1NC). The N4-vacancy-rich porous carbon (V-NC) renders multiple merits: (1) a high N content of 13.94 atom % for large Li-storage capacity, (2) edged unsaturated N sites favoring highly efficient Li+ adsorption and desolvation, and (3) a shortening of the Li+ diffusion length through N4 vacancy, thereby enhancing the Li-storage kinetics and high-rate performance. This work serves as an inspiration for the creation of heteroatom-edged porous structures with controllable pore sizes for high-rate alkali-ion battery applications.

Strongly coupled Fe-doped NiS2/MoS2 composite for high-efficiency water splitting.

We developed a simple method to fabricate a strongly coupled Fe-doped NiS2/MoS2 composite by introducing dual confinement effects during the vapor vulcanization of precursors, which involves the controlled release of metal species and the in situ formation of an N-doped carbon layer. The Fe-doped NiS2/MoS2 composite exhibited a much-enhanced hydrogen/oxygen evolution reaction performance.

Formamide-derived "glue" for the hundred-gram scale synthesis of atomically dispersed iron-nitrogen-carbon electrocatalysts.

The distinct structure and maximum utilization of metal atoms on supported single-atom catalysts (SACs) represents a new frontier of heterogeneous catalysis, yet the low-cost mass production of high-performance SACs is still a key issue for practical applications. Herein, by coating a formamide-derived highly N-modified carbonaceous layer as a "glue" on commercially available activated carbon black (AC), a hundred-gram scale synthesis of atomically dispersed non-noble metal-nitrogen-carbon (MNC) materials was realized, including but not limited to Fe, Co, Ni, Mn, and Cu. The dispersion and coordination environments of Fe atoms on AC were initially revealed by XRD, HRTEM, and XPS, and further confirmed by HAADF-STEM and XANES analysis, presenting Fe atoms in a Fe-N4 structure. The atomically dispersed metal species, though relatively low-loading grafted on AC (typical loading of 0.16 to 0.29 at%), are mostly distributed on the electrochemically accessible surface, resulting in improved metal utilization. The FeNC@AC-3 sample exhibited highly comparable catalytic performance to 20 wt% Pt/C for the alkaline oxygen reduction reaction, and superior Al-air battery performance. Our work may inspire the synthesis of other types of SACs for broad electrocatalysis applications at kilogram or even ton scale.

Accurately Regulating the Electronic Structure of Nix Sey @NC Core-Shell Nanohybrids through Controllable Selenization of a Ni-MOF for pH-Universal Hydrogen Evolution Reaction.

N-doped carbon-encapsulated transition metal selenides (TMSs) have garnered increasing attention as promising electrocatalysts for hydrogen evolution reaction (HER). Accurately regulating the electronic structure of these nanohybrids to reveal the underlying mechanism for enhanced HER performances is still challenging and thus requires deep excavation. Herein, a series of pomegranate-like Nix Sey @NC core-shell nanohybrids (including Ni0.85 Se @ NC, NiSe2 @NC, and NiSe@NC) through controllable selenization of a Ni-MOF precursor is reported. The component of the nanohybrids can be fine-tuned by tailoring the selenization temperature and feed ratio, through which the electronic structure can be synchronously regulated. Among these nanohybrids, the Ni0.85 Se @ NC exhibits the optimum pH-universal HER performance with overpotentials of 131, 135, and 183 mV in 0.5 m H2 SO4 , 1.0 m KOH, and 1.0 m PBS, respectively, at 10 mA cm-2 , which are attributed to the increased partial density of state at the Fermi level and effective van der Waals interactions between Ni0.85 Se and NC matrix explained by density functional theory calculations.

A channel-structured Eu-based metal-organic framework with a zwitterionic ligand for selectively sensing Fe3+ ions.

A novel Eu-based MOF [Eu(IMS1)2]Cl·4H2O (1) was successfully constructed based on a semi-rigid zwitterionic 1,3-bis(4-carboxylbenzyl)-imidazolium (IMS1) ligand, featuring a 3-fold interpenetrating dia net structure with a point symbol of 66 and charged permanent micropores. Considering its excellent luminescent property as well as thermal and chemical stability, complex 1 was explored as a potential sensor for detecting Fe3+ ions. The results show that complex 1 has a high sensitivity and selectivity for Fe3+ based on a 'turn-off' effect, for which the electrostatic interaction between Fe3+ ions and the inner surface of the micropores may play a critical role. The fluorescence quenching mechanism reveals that dynamic quenching and competitive adsorption between Fe3+ and 1 lead to the quenching effect of 1.