Bifunctional interstitial phosphorous doping strategy boosts platinum-zinc alloy for efficient ammonia oxidation reaction and hydrogen evolution reaction

It is still a lack of bifunctional catalysts for ammonia oxidation reaction(AOR)and hydrogen evolution reaction(HER)due to their different reaction mechanisms.In this work,P is doped into PtZn alloy by calcination with NaH_(2)PO_(2) as P source to induce the lattice tensile strain of Pt and the electronic interaction between P and Zn,which optimizes the AOR and HER activity simultaneously.The sample with the optimal P content can drive the AOR peak current density of 293.6 mA·mgPt^(-1),which is almost 2.7 times of Pt.For HER,the overpotential at^(-1)0 mA·cm^(-2) is only 23 mV with Tafel slope of 34.1 mV·dec^(-1).Furthermore,only 0.59 V is needed to obtain 50 mA·mgPt^(-1) for ammonia electrolysis under a two-electrode system.Therefore,this work shows an ingenious method to design bifunctional catalysts for ammonia electrolysis.

Investigation of cubic Pt alloys for ammonia oxidation reaction

As a promising fuel candidate,ammonia has been successtully used as anode feed in alkaline fuel cells.However,current technology in catalysts for ammonia electro-oxidation reaction(AOR)with respect to both cost and performance is inadequate to ensure large scale commercial application of direct ammonia fuel cells.Recent studies found that alloying Pt with different transition metals and controlling the morphology of catalysts can improve the AOR activity,and thus potentially can solve the cost issue.Herein,(100)-terminated Pt-M nanocubes(M=3d-transition metals Fe,Co,Ni,Zn)are synthesized via wet-chemistry method and their catalytic activities toward AOR are evaluated.The addition of Fe,Co,Ni and Zn elements can enhance the AOR activity due to decrease in oxophilicity of platinum and bifunctional mechanism.Pt-Zn exhibits the maximum mass activity and specific ativity with values of 0.41 A/mgpt and 169 mA/cm2 that are 1.6 and 1.8 times higher than Pt nanocubes,respectively.Pt-Fe,Pt-Co and PI-Ni nanocubes also ilustrate higher mass and specific activities compared to Pt nanocubes.

Activating copper oxide for stable electrocatalytic ammonia oxidation reaction via in-situ introducing oxygen vacancies

Electrocatalytic ammonia oxidation reaction(EAOR)provides an ideal solution for on-board hydrogen supply for fuel cells,while the lack of efficient and durable EAOR catalysts has been a long-standing obstacle for its practical application.Herein,we reported that the defect engineering via in-situ electrochemically introducing oxygen vacancies(Vo)not only turns the inactive CuO into efficient EAOR catalyst but also achieves a high stability of over 400 h at a high current density of~200 mA·cm^(−2).Theoretical simulation reveals that the presence of Vo on the CuO surface induces a remarkable upshift of the d-band center of active Cu site closer to the Fermi level,which significantly stabilizes the reaction intermediates(*NHx)and efficiently oxidizes NH3 into N2.This Vo-modulated CuO shows a different catalytic mechanism from that on the conventional Pt-based catalysts,paving a new avenue to develop inexpensive,efficient,and robust catalysts,not limited to EAOR.

Hydrogen generation from ammonia electrolysis on bifunctional platinum nanocubes electrocatalysts

The ammonia electrolysis is a highly efficient and energy-saving method for ultra-pure hydrogen generation, which highly relies on electrocatalytic performance of electrocatalysts. In this work, high-quality platinum(Pt) nanocubes(Pt-NCs) with 4.5 nm size are achieved by facile hydrothermal synthesis. The physical morphology and structure of Pt-NCs are exhaustively characterized, revealing that Pt-NCs with special {100} facets have excellent uniformity, good dispersity and high crystallinity. Meanwhile, the electrocatalytic performance of Pt-NCs for ammonia electrolysis are carefully investigated in alkaline solutions, which display outstanding electroactivity and stability for both ammonia electrooxidation reaction(AEOR) and hydrogen evolution reaction(HER) in KOH solution. Furthermore, a symmetric Pt-NCs||Pt-NCs ammonia electrolyzer based on bifunctional Pt-NCs electrocatalyst is constructed, which only requires 0.68 V electrolysis voltage for hydrogen generation. Additionally, the symmetric Pt-NCs||Pt-NCs ammonia electrolyzer has excellent reversible switch capability for AEOR at anode and HER at cathode, showing outstanding alternating operation ability for ammonia electrolysis.

Arrayed Cobalt Phosphide Electrocatalyst Achieves Low Energy Consumption and Persistent H2 Liberation from Anodic Chemical Conversion

Electrochemical reduction of water to hydrogen(H2) offers a promising strategy for production of clean energy,but the design and optimization of electrochemical apparatus present challenges in terms of H2 recovery and energy consumption.Using cobalt phosphide nanoarrays(Co2 P/CoP NAs) as a charge mediator,we effectively separated the H2 and O2 evolution of alkaline water electrolysis in time,thereby achieving a membrane-free pathway for H2 purification.The hierarchical array structure and synergistic optimization of the electronic configuration of metallic Co2 P and metalloid CoP make the Co2 P/CoP NAs high-efficiency bifunctional electrocatalysts for both charge storage and hydrogen evolution.Theoretical investigations revealed that the introduction of Co2 P into CoP leads to a moderate hydrogen adsorption free energy and low water dissociation barrier,which are beneficial for boosting HER activity.Meanwhile,Co2 P/CoP NAs with high capacitance could maintain a cathodic H2 evolution time of 1500 s at 10 mA cm^(-2) driven by a low average voltage of 1.38 V.Alternatively,the energy stored in the mediator could be exhausted via coupling with the anodic oxidation of ammonia,whereby only 0.21 V was required to hold the current for 1188 s.This membrane-free architecture demonstrates the potential for developing hydrogen purification technology at low cost.

Theoretical studies on ammonia oxide and its unimolecular reactions

The unimolccular reactions of ammonia oxide H_3NO,isomerization and dehydrogenation, are investigated by ab initio MO calculations with the 4-31G basis set.The geometries and energies of the reactant,transition states and products have been determined on the singlet potential energy sur- face.The reaction ergodography along the intrinsic reaction coordinate(IRC)for the two reactions have been performed.The vibrational frequency correlation diagram of the two reactions are analyzed along the IRC.