Co/CoS2 Heterojunction Embedded in N, S-Doped Hollow Nanocage for Enhanced Polysulfides Conversion in High-Performance Lithium-Sulfur Batteries.

Modulating the electronic configuration of the substrate to achieve the optimal chemisorption toward polysulfides (LiPSs) for boosting polysulfide conversion is a promising way to the efficient Li-S batteries but filled with challenges. Herein, a Co/CoS2 heterostructure is elaborately built to tuning d-orbital electronic structure of CoS2 for a high-performance electrocatalyst. Theoretical simulations first evidence that Co metal as the electron donator can form a built-in electric field with CoS2 and downshift the d-band center, leading to the well-optimized adsorption strength for lithium polysulfides on CoS2 , thus contributing a favorable way for expediting the redox reaction kinetics of LiPSs. As verification of prediction, a Co/CoS2 heterostructure implanted in porous hollow N, S co-doped carbon nanocage (Co/CoS2 @NSC) is designed to realize the electronic configuration regulation and promote the electrochemical performance. Consequently, the batteries assembled with Co/CoS2 @NSC cathode display an outstanding specific capacity and an admirable cycling property as well as a salient property of 8.25 mAh cm-2 under 8.18 mg cm-2 . The DFT calculation also reveals the synergistic effect of N, S co-doping for enhancing polysulfide adsorption as well as the detriment of excessive sulfur doping.

Controllable Electronic Transfer Tailoring d-band Center via Cobalt-Oxygen-Bridged Ru/Fe Dual-sites for Boosted Oxygen Evolution.

Rational tailoring of the electronic structure at the defined active center of reconstructed metal (oxy)hydroxides (MOOH) during oxygen evolution reaction (OER) remains a challenge. With the guidance of density functional theory (DFT), herein a dual-site regulatory strategy is reported to tailor the d-band center of the Co site in CoOOH via the controlled electronic transfer at the Ru─O─Co─O─Fe bonding structure. Through the bridged O2- site, electrons are vastly flowed from the t2g-orbital of the Ru site to the low-spin orbital of the Co site in the Ru-O-Co coordination and further transfer from the strong electron-electron repulsion of the Co site to the Fe site by the Co-O-Fe coordination, which balancing the electronic configuration of Co sites to weaken the over-strong adsorption energy barrier of OH* and O*, respectively. Benefiting from the highly active of the Co site, the constructed (Ru2Fe2Co6)OOH provide an extremely low overpotential of 248 mV and a Tafel slope of 32.5 mV dec-1 at 10 mA cm-2 accompanied by long durability in alkaline OER, far superior over the pristine and Co-O-Fe bridged CoOOH catalysts. This work provides guidance for the rational design and in-depth analysis of the optimized role of metal dual-sites.

Directed Dual Charge Pumping Tunes the d-Orbital Configuration of Pt Cluster Boosting Hydrogen Evolution Kinetic.

Achieving high catalytic activity with a minimum amount of platinum (Pt) is crucial for accelerating the cathodic hydrogen evolution reaction (HER) in proton exchange membrane (PEM) water electrolysis, yet it remains a significant challenge. Herein, a directed dual-charge pumping strategy to tune the d-orbital electronic distribution of Pt nanoclusters for efficient HER catalysis is proposed. Theoretical analysis reveals that the ligand effect and electronic metal-support interactions (EMSI) create an effective directional electron transfer channel for the d-orbital electrons of Pt, which in turn optimizes the binding strength to H*, thereby significantly enhancing HER efficiency of the Pt site. Experimentally, this directed dual-charge pumping strategy is validated by elaborating Sb-doped SnO2 (ATO) supported Fe-doped PtSn heterostructure catalysts (Fe-PtSn/ATO). The synthesized 3%Fe-PtSn/ATO catalysts exhibit lower overpotential (requiring only 10.5 mV to reach a current density of 10 mA cm- 2), higher mass activity (28.6 times higher than commercial 20 wt.% Pt/C), and stability in the HER process in acidic media. This innovative strategy presents a promising pathway for the development of highly efficient HER catalysts with low Pt loading.

Optimizing Intermediate Adsorption on Pt Sites via Triple-Phase Interface Electronic Exchange for Methanol Oxidation.

For the most commonly applied platinum-based catalysts of direct methanol fuel cells, the adsorption ability toward reaction intermediates, including CO and OH, plays a vital role in their catalytic activity and antipoisoning in anodic methanol oxidation reaction (MOR). Herein, guided by a theoretical mechanism study, a favorable modulation of the electronic structure and intermediate adsorption energetics for Pt active sites is achieved by constructing the triple-phase interfacial structure between tin oxide (SnO2), platinum (Pt), and nitrogen-doped graphene (NG). From the strong electronic exchange at the triple-phase interface, the adsorption ability toward MOR reaction intermediates on Pt sites could be efficiently optimized, which not only inhibits the adsorption of CO* on active sites but also facilitates the adsorption of OH* to strip the poisoning species from the catalyst surface. Accordingly, the resulting catalyst delivers excellent catalytic activity and antipoisoning ability for MOR catalysis. The mass activity reaches 1098 mA mg-1Pt, 3.23 times of commercial Pt/C. Meanwhile, the initial potentials and main peak for CO oxidation are also located at a much lower potential (0.51 and 0.74 V) against commercial Pt/C (0.83 and 0.89 V).

Optimizing d-Orbital Electronic Configuration via Metal-Metal Oxide Core-Shell Charge Donation for Boosting Reversible Oxygen Electrocatalysis.

Tuning the d-orbital electronic configuration of active sites to achieve well-optimized adsorption strength of oxygen-containing intermediates toward reversible oxygen electrocatalysis is desirable for efficient rechargeable Zn-Air batteries but extremely challenging. Herein, this work proposes to construct a Co@Co3 O4 core-shell structure to regulate the d-orbital electronic configuration of Co3 O4 for the enhanced bifunctional oxygen electrocatalysis. Theoretical calculations first evidence that electron donation from Co core to Co3 O4 shell could downshift the d-band center and simultaneously weak spin state of Co3 O4 , result in the well-optimized adsorption strength of oxygen-containing intermediates on Co3 O4 , thus contributing a favor way for oxygen reduction/evolution reaction (ORR/OER) bifunctional catalysis. As a proof-of-concept, the Co@Co3 O4 embedded in Co, N co-doped porous carbon derived from thickness controlled 2D metal-organic-framework is designed to realize the structure of computational prediction and further improve the performance. The optimized 15Co@Co3 O4 /PNC catalyst exhibits the superior bifunctional oxygen electrocatalytic activity with a small potential gap of 0.69 V and a peak power density of 158.5 mW cm-2 in ZABs. Moreover, DFT calculations shows that the more oxygen vacancies on Co3 O4 contribute too strong adsorption of oxygen intermediates which limit the bifunctional electrocatalysis, while electron donation in the core-shell structure can alleviate the negative effect and maintain superior bifunctional overpotential.

Tailored Lattice Compressive Strain of Pt-Skins by the L12 -Pt3 M Intermetallic Core for Highly Efficient Oxygen Reduction.

The sluggish kinetics of oxygen reduction reaction (ORR) and unsatisfactory durability of Pt-based catalysts are severely hindering the commercialization of proton-exchange-membrane fuel cells (PEMFCs). In this work, the lattice compressive strain of Pt-skins imposed by Pt-based intermetallic cores is tailored for highly effective ORR through the confinement effect of the activated nitrogen-doped porous carbon (a-NPC). The modulated pores of a-NPC not only promote Pt-based intermetallics with ultrasmall size (average size of <4 nm), but also efficiently stabilizes intermetallic nanoparticles and sufficient exposure of active sites during the ORR process. The optimized catalyst (L12 -Pt3 Co@ML-Pt/NPC10 ) achieves excellent mass activity (1.72 A mgPt -1 ) and specific activity (3.49 mA cmPt -2 ), which are 11- and 15-fold that of commercial Pt/C, respectively. Besides, owing to the confinement effect of a-NPC and protection of Pt-skins, L12 -Pt3 Co@ML-Pt/NPC10 retains 98.1% mass activity after 30 000 cycles, and even 95% for 100 000 cycles, while Pt/C retains only 51.2% for 30 000 cycles. Rationalized by density functional theory, compared with other metals (Cr, Mn, Fe, and Zn), L12 -Pt3 Co closer to the top of "volcano" induces a more suitable compressive strain and electronic structure on Pt-skin, leading to an optimal oxygen adsorption energy and a remarkable ORR performance.

Dual roles of sub-nanometer NiO in alkaline hydrogen evolution reaction: breaking the Volmer limitation and optimizing d-orbital electronic configuration.

Pt-based nanoclusters toward the hydrogen evolution reaction (HER) remain the most promising electrocatalysts. However, the sluggish alkaline Volmer-step kinetics and the high-cost have hampered progress in developing high-performance HER catalysts. Herein, we propose to construct sub-nanometer NiO to tune the d-orbital electronic structure of nanocluster-level Pt for breaking the Volmer-step limitation and reducing the Pt-loading. Theoretical simulations firstly suggest that electron transfer from NiO to Pt nanoclusters could downshift the Ed-band of Pt and result in the well-optimized adsorption/desorption strength of the hydrogen intermediate (H*), therefore accelerating the hydrogen generation rate. NiO and Pt nanoclusters confined into the inherent pores of N-doped carbon derived from ZIF-8 (Pt/NiO/NPC) were designed to realize the structure of computational prediction and boost the alkaline hydrogen evolution. The optimal 1.5%Pt/NiO/NPC exhibited an excellent HER performance and stability with a low Tafel slope (only 22.5 mv dec-1) and an overpotential of 25.2 mV at 10 mA cm-2. Importantly, the 1.5%Pt/NiO/NPC possesses a mass activity of 17.37 A mg-1 at the overpotential of 20 mV, over 54 times higher than the benchmark 20 wt% Pt/C. Furthermore, DFT calculations illustrate that the Volmer-step could be accelerated owing to the high OH- attraction of NiO nanoclusters, leading to the Pt nanoclusters exhibiting a balance of H* adsorption and desorption (ΔGH* = -0.082 eV). Our findings provide new insights into breaking the water dissociation limit of Pt-based catalysts by coupling with a metal oxide.

Polyaniline-functionalized carbon nanotube supported platinum catalysts.

Electrocatalytically active platinum (Pt) nanoparticles on a carbon nanotube (CNT) with enhanced nucleation and stability have been demonstrated through introduction of electron-conducting polyaniline (PANI) to bridge the Pt nanoparticles and CNT walls with the presence of platinum-nitride (Pt-N) bonding and π-π bonding. The Pt colloids were prepared through ethanol reduction under the protection of aniline, the CNT was dispersed well with the existence of aniline in the solution, and aniline was polymerized in the presence of a protonic acid (HCl) and an oxidant (NH(4)S(2)O(8)). The synthesized PANI is found to wrap around the CNT as a result of π-π bonding, and highly dispersed Pt nanoparticles are loaded onto the CNT with narrowly distributed particle sizes ranging from 2.0 to 4.0 nm due to the polymer stabilization and existence of Pt-N bonding. The Pt-PANI/CNT catalysts are electroactive and exhibit excellent electrochemical stability and therefore promise potential applications in proton exchange membrane fuel cells.

Pt3Sn nanoparticles enriched with SnO2/Pt3Sn interfaces for highly efficient alcohol electrooxidation.

Pt3Sn nanoparticles (NPs) enriched with Pt3Sn/ultra-small SnO2 interfaces (Pt3Sn@u-SnO2/NG) were synthesized through a thermal treatment of Pt2Sn/NG in a H2 atmosphere, followed by annealing under H2 and air conditions. The unique structure of Pt3Sn NPs enriched with Pt3Sn/SnO2 interfaces was observed on the Pt3Sn@u-SnO2/NG catalyst based on HRTEM. The optimized Pt3Sn@u-SnO2/NG catalyst achieves high catalytic activity with an ethanol oxidation reaction (EOR) activity of 366 mA mgPt -1 and a methanol oxidation reaction (MOR) activity of 503 mA mgPt -1 at the potential of 0.7 V, which are eight-fold and five-fold higher than those for the commercial Pt/C catalyst (44 and 99 mA mgPt -1, respectively). The Pt3Sn@u-SnO2/NG catalyst is found to be 3 times more stable and have higher CO tolerance than Pt/C. The outstanding performance of the Pt3Sn@u-SnO2/NG catalyst should be ascribed to the synergetic effect induced by the unique structure of Pt3Sn NPs enriched with Pt3Sn/SnO2 interfaces. The synergetic effect between Pt3Sn NPs and ultra-small SnO2 increases the performance for alcohol oxidation because the Sn in both Pt3Sn and SnO2 favors the removal of COads on the nearby Pt by providing OHads species at low potentials. The present work suggests that the Pt3Sn@u-SnO2 is indeed a unique kind of efficient electrocatalyst for alcohol electrooxidation.

Enhancement of the performance of Pd nanoclusters confined within ultrathin silica layers for formic acid oxidation.

The optimized design of highly active and stable anode electrocatalysts is essential for high performance direct formic acid fuel cells (DFAFCs). Herein, a facile and cost-effective strategy was proposed to fabricate a robust ultrasmall Pd nanocluster confined within ultrathin protective silica layers anchored on nitrogen doped reduced GO (NrGO) through generating amine functionalized graphene oxide with 3-aminopropyl triethoxysilane (APTES), followed by tuning the thickness of protective silica layers by precisely controlling the amount of tetraethylorthosilicate (TEOS). Amine functionalized graphene oxide generated by using APTES favors the formation of ultrasmall Pd nanoclusters due to the coordination of amine to PdCl24- while the confinement effect of ultrathin protective silica layers stabilizes ultrasmall Pd nanoclusters and impedes the agglomeration and sintering of ultrasmall Pd nanoclusters during electrocatalysis. As a result, the ultrasmall Pd nanoclusters (∼1.4 nm) confined in silica layers on NrGO (Pd/NrGO@SiO2) demonstrate a very high forward peak current density for formic acid oxidation (FAO) of 2.37 A mg-1, outperforming the Pd/C catalyst (0.30 A mg-1) and the Pd/rGO catalyst obtained by a conventional method (0.42 A mg-1). More importantly, our confined Pd catalysts show the highest stability of only 5% inconspicuous degradation of the initial mass activity after 1000 cycles, compared with Pd/C (almost 100% loss), Pd/rGO (61.5% loss) and Pd/NrGO (73.2% loss). These strategies in this work provide a new prospect for the design of excellent noble catalysts to overcome the challenges in the practical application of DFAFCs.

Encapsulating Pt Nanoparticles inside a Derived Two-Dimensional Metal-Organic Frameworks for the Enhancement of Catalytic Activity.

The development of highly active and stable electrocatalysts toward oxygen reduction reaction (ORR) and hydrogen evolution reaction (HER) is a key for commercial application of fuel cells and water splitting. Here, we report a highly active and stable Pt nanoparticles (NPs) encapsulated in ultrathin two-dimensional (2D) carbon layers derived from the ultrathin 2D metal-organic framework precursor (ZIF-67). Electrochemical tests reveal that our approach not only stabilized Pt NPs successfully but also boosted Pt activities toward ORR and HER. We found that our Pt catalysts encapsulated in ultrathin 2D carbon layers exhibited an ORR activity of 5.9 and 12 times greater than those of the commercial Pt/C and Pt/RGO without 2D carbon layer protection. Our encapsulated Pt catalysts also show more than nine times higher stability than those of Pt/C catalysts. In addition to ORR, our novel encapsulated Pt catalysts display an extraordinary stability and activity toward HER, with a lower overpotential (14.3 mV in acidic media and 37.2 mV in alkaline media) at a current density of 10 mA cm-2 than Pt/C catalysts (23.1 mV in acidic media and 92.1 mV in alkaline media). The enhanced electrochemical activities and stability of our encapsulated Pt catalysts are attributed to the synergistic effect of Pt-based NPs and ultrathin 2D carbon layers derived from ZIF-67 with enriched active sites Co-Nx. First-principles simulations reveal that the synergistic catalysis of Pt-based NPs and Co-Nx derived from ZIF-67 improves the activity for ORR and HER.

Highly Active and Durable Ultrasmall Pd Nanocatalyst Encapsulated in Ultrathin Silica Layers by Selective Deposition for Formic Acid Oxidation.

The low performance of palladium (Pd) is a considerable challenge for direct formic acid fuel cells in practical applications. Herein, we develop a simple strategy to synthesize a highly active and durable Pd nanocatalyst encapsulated in ultrathin silica layers with vertically aligned nanochannels covered graphene oxides (Pd/rGO@pSiO2) without blocking active sites by selective deposition. The Pd/rGO@pSiO2 catalyst exhibits very high performance for a formic acid oxidation (FAO) reaction compared with the Pd/rGO without protective silica layers and commercial Pd/C catalysts. Pd/rGO@pSiO2 shows an FAO activity 3.9 and 3.8 times better than those of Pd/rGO and Pd/C catalysts, respectively. The Pd/rGO@pSiO2 catalysts are also almost 6-fold more stable than Pd/C and more than 3-fold more stable than Pd/rGO. The outstanding performance of our encapsulated Pd catalysts can be ascribed to the novel design of nanostructures by selective deposition fabricating ultrasmall Pd nanoparticles encapsulated in ultrathin silica layers with vertically aligned nanochannels, which not only avoid blocking the active sites but also facilitate the mass transfer in encapsulated catalysts. Our work indicates an important method to the rational design of high-performance catalysts for fuel cells in practical applications.

Structurally ordered PtSn intermetallic nanoparticles supported on ATO for efficient methanol oxidation reaction.

The development of cost-effective methanol oxidation reaction (MOR) catalysts with a high activity and stability is highly desirable for direct methanol fuel cells. In this study, the structurally ordered PtSn intermetallic nanoparticles supported on Sb-doped SnO2 (ATO) have been successfully synthesized in ethylene glycol (EG) solution at 200 °C. Pt NPs were firstly formed on ATO, followed by the transformation from Pt into hexagonal PtSn on the surface of ATO. The obtained structurally ordered PtSn intermetallic NPs supported on ATO demonstrate significantly enhanced MOR activity and durability in comparison with commercial Pt/C. Our PtSn intermetallic NPs supported on ATO show a MOR activity 4.1 times higher than that of commercial Pt/C catalysts. Accelerated durability tests indicate that the commercial Pt/C catalysts lose about 50% of their initial current density after 500 cycles while the Pt/ATO-200-3 h catalyst loses only about 15% of its initial current density. Our PtSn intermetallic NPs supported on ATO are also found to have higher CO tolerance than commercial Pt/C. This work demonstrates an important strategy to rationally design high-performance structurally ordered Pt-based intermetallic NP catalysts for fuel cells and other applications.

Platinum single-atom and cluster catalysis of the hydrogen evolution reaction.

Platinum-based catalysts have been considered the most effective electrocatalysts for the hydrogen evolution reaction in water splitting. However, platinum utilization in these electrocatalysts is extremely low, as the active sites are only located on the surface of the catalyst particles. Downsizing catalyst nanoparticles to single atoms is highly desirable to maximize their efficiency by utilizing nearly all platinum atoms. Here we report on a practical synthesis method to produce isolated single platinum atoms and clusters using the atomic layer deposition technique. The single platinum atom catalysts are investigated for the hydrogen evolution reaction, where they exhibit significantly enhanced catalytic activity (up to 37 times) and high stability in comparison with the state-of-the-art commercial platinum/carbon catalysts. The X-ray absorption fine structure and density functional theory analyses indicate that the partially unoccupied density of states of the platinum atoms' 5d orbitals on the nitrogen-doped graphene are responsible for the excellent performance.

Extremely stable platinum nanoparticles encapsulated in a zirconia nanocage by area-selective atomic layer deposition for the oxygen reduction reaction.

Encapsulation of Pt nanoparticles (NPs) in a zirconia nanocage by area-selective atomic layer deposition (ALD) can significantly enhance both the Pt stability and activity. Such encapsulated Pt NPs show 10 times more stability than commercial Pt/C catalysts and an oxygen reduction reaction (ORR) activity 6.4 times greater than that of Pt/C.

Highly active Pt@Au nanoparticles encapsulated in perfluorosulfonic acid for the reduction of oxygen.

The Pt@Au catalysts demonstrate remarkably high oxygen reduction reaction (ORR) activity compared with Pt/C catalysts. The ORR of Pt(2)@Au(1)/C and Pt(1)@Au(2)/C is 9.5 and 6.6 times that of Pt/C, respectively. This improvement is attributed to the electronic structure effect of the Au core on the Pt shell and introduction of PFSA.