Designing 3d Transition Metal Cation-Doped MRuOx As Durable Acidic Oxygen Evolution Electrocatalysts for PEM Water Electrolyzers.

The continuous dissolution and oxidation of active sites in Ru-based electrocatalysts have greatly hindered their practical application in proton exchange membrane water electrolyzers (PEMWE). In this work, we first used density functional theory (DFT) to calculate the dissolution energy of Ru in the 3d transition metal-doped MRuOx (M = Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, and Zn) to evaluate their stability for acidic oxygen evolution reaction (OER) and screen out ZnRuOx as the best candidate. To confirm the theoretical predictions, we experimentally synthesized these MRuOx materials and found that ZnRuOx indeed displays robust acidic OER stability with a negligible decay of η10 after 15 000 CV cycles. Of importance, using ZnRuOx as the anode, the PEMWE can run stably for 120 h at 200 mA cm-2. We also further uncover the stability mechanism of ZnRuOx, i.e., Zn atoms doped in the outside of ZnRuOx nanocrystal would form a "Zn-rich" shell, which effectively shortened average Ru-O bond lengths in ZnRuOx to strengthen the Ru-O interaction and therefore boosted intrinsic stability of ZnRuOx in acidic OER. In short, this work not only provides a new study paradigm of using DFT calculations to guide the experimental synthesis but also offers a proof-of-concept with 3d metal dopants as RuO2 stabilizer as a universal principle to develop high-durability Ru-based catalysts for PEMWE.

A general descriptor for single-atom catalysts decorated with axial ligand.

Decoration of an axial coordination ligand (ACL) on the active metal site is a highly effective and versatile strategy to tune activity of single-atom catalysts (SACs). However, the regulation mechanism of ACLs on SACs is still incompletely known. Herein, we investigate diversified combinations of ACL-SACs, including all 3d-5d transition metals and ten prototype ACLs. We identify that ACLs can weaken the adsorption capability of the metal atom (M) by raising the bonding energy levels of the M-O bond while enhancing dispersity of the d orbital of M. Through examination of various local configurations and intrinsic parameters of ACL-SACs, a general structure descriptor σ is constructed to quantify the structure-activity relationship of ACL-SACs which solely based on a few key intrinsic features. Importantly, we also identified the axial ligand descriptor σACL, as a part of σ, which can serve as a potential descriptor to determine the rate-limiting steps (RLS) of ACL-SACs in experiment. And we predicted several ACL-SACs, namely, CrN4-, FeN4-, CoN4-, RuN4-, RhN4-, OsN4-, IrN4- and PtN4-ACLs, that entail markedly higher activities than the benchmark catalysts of Pt and IrO2, thereby supporting that the general descriptor σ can provide a simple and cost-effective method to assess efficient electrocatalysts.

Molecular Engineering for Modulating Photocatalytic Hydrogen Evolution of Fully Conjugated 3D Covalent Organic Frameworks.

Covalent organic frameworks (COFs) have recently shown great potential for photocatalytic hydrogen production. Currently almost all reports are focused on two-dimensional (2D) COFs, while the 3D counterparts are rarely explored due to their non-conjugated frameworks derived from the sp3 carbon based tetrahedral building blocks. Here, we rationally designed and synthesized a series of fully conjugated 3D COFs by using the saddle-shaped cyclooctatetrathiophene derivative as the building block. Through molecular engineering strategies, we thoroughly discussed the influences of key factors including the donor-acceptor structure, hydrophilicity, specific surface areas, as well as the conjugated/non-conjugated structures on their photocatalytic hydrogen evolution properties. The as-synthesized fully conjugated 3D COFs could generate the hydrogen up to 40.36 mmol h-1 g-1. This is the first report on intrinsic metal-free 3D COFs in photocatalytic hydrogen evolution application. Our work provides insight on the structure design of 3D COFs for highly-efficient photocatalysis, and also reveals that the semiconducting fully conjugated 3D COFs could be a useful platform in clear energy-related fields.

Designing Thiophene-Enriched Fully Conjugated 3D Covalent Organic Framework as Metal-Free Oxygen Reduction Catalyst for Hydrogen Fuel Cells.

The application of three-dimensional (3D) covalent organic frameworks (COFs) in renewable energy fields is greatly limited due to their non-conjugated skeletons. Here, we design and successfully synthesize a thiophene-enriched fully conjugated 3D COF (BUCT-COF-11) through an all-thiophene-linked saddle-shaped building block (COThTh-CHO). The BUCT-COF-11 exhibits excellent semiconducting property with intrinsic metal-free oxygen reduction reaction (ORR) activity. Using the COF as cathode catalyst, the assembled anion-exchange membrane fuel cells (AEMFCs) exhibited a high peak power density up to 493 mW cm-2 . DFT calculations reveal that thiophene introduction in the COF not only improves the conductivity but also optimizes the electronic structure of the sample, which therefore boosts the ORR performance. This is the first report on the application of COFs as metal-free catalysts in fuel cells, demonstrating the great potential of fully conjugated 3D COFs as promising semiconductors in energy fields.

Multicomponent Synthesis of Imidazole-Linked Fully Conjugated 3D Covalent Organic Framework for Efficient Electrochemical Hydrogen Peroxide Production.

The semiconducting properties and applications of three dimensional (3D) covalent organic frameworks (COFs) are greatly hampered because of their long-ranged non-conjugated skeletons and relatively unstable linkages. Here, a robust imidazole-linked fully conjugated 3D covalent organic framework (BUCT-COF-7) is synthesized through the one-pot multicomponent Debus-Radziszewski reaction of the saddle-shaped aldehyde-substituted cyclooctatetrathiophene, pyrene-4,5,9,10-tetraone, and ammonium acetate. The semiconducting BUCT-COF-7, as a metal-free catalyst, shows excellent two electron oxygen reduction reaction (ORR) activity in alkaline medium with high hydrogen peroxide (H2 O2 ) selectivity of 83.4 %. When the BUCT-COF-7 as cathode catalyst is assembled into the electrolyzer, the devices showed high electrochemical production rate of H2 O2 up to 326.9 mmol g-1 h-1 . The accumulative amount of H2 O2 could totally degrade the dye methylene blue via Fenton reaction for wastewater treatment. This is the first report about intrinsic 3D COFs for efficient electrochemical synthesis of H2 O2 , revealing the promising applications of fully conjugated 3D COFs in the environment-related field.

Atomically Dispersed Zn-Pyrrolic-N4 Cathode Catalysts for Hydrogen Fuel Cells.

To achieve practical application of fuel cell, it is vital to develop highly efficient and durable Pt-free catalysts. Herein, we prepare atomically dispersed ZnNC catalysts with Zn-Pyrrolic-N4 moieties and abundant mesoporous structure. The ZnNC-based anion-exchange membrane fuel cell (AEMFC) presents an ultrahigh peak power density of 1.63 and 0.83 W cm-2 in H2 -O2 and H2 -air (CO2 -free), and also exhibits long-term stability with more than 120 and 100 h for H2 -air (CO2 -free) and H2 -O2 , respectively. Density functional calculations further unveil that the Zn-Pyrrolic-N4 structure is the origin of high activity of as-synthesized ZnNC catalyst, while the Zn-Pyridinic-N4 moiety is inactive for oxygen reduction reaction (ORR), which successfully explain the puzzle why most Zn-metal-organic framework -derived ZnNC catalysts in previous reports did not present good ORR activity because of their Zn-Pyridinic-N4 moieties. This work offers a new route for speeding up development of AEMFCs.

Robust Ru-VO2 Bifunctional Catalysts for All-pH Overall Water Splitting.

Designing robust bifunctional catalysts for oxygen evolution reaction (OER) and hydrogen evolution reaction in all-pH conditions for overall water splitting (OWS) is an effective way to achieve sustainable development. Herein, a composite Ru-VO2 containing Ru-doped VO2 and Ru nanoparticles (NPs) is synthesized, and it shows a high OWS performance in full-pH range due to their synergist effect. In particular, the OER mass activities of Ru-VO2 at 1.53 V (vs RHE) in acidic, alkaline, and PBS solutions are ≈65, 36, and 235 times of commercial RuO2 in the same conditions. The "Ru-VO2 || Ru-VO2 " two-electrode electrolyzer only needs a voltage of 1.515 V (at 10 mA cm-2 ) in acidic water splitting, which can operate stably for 125 h at 10 mA cm-2 without significant voltage decay. In situ Raman spectra and in situ differential electrochemical mass spectrometry prove that the OER of Ru-VO2 in acid follows the adsorption evolution mechanism. Density functional theory calculations further reveal the synergistic effect between Ru NP and Ru-doped VO2 , which breaks the hydrogen bond network formed by *OH adsorbed on the Ru single-atom site, and thereby significantly enhances the OER activity. This work provides new insights into the design of novel bifunctional pH-universal catalysts for OWS.

Novel 2D carbon material T-graphene supported 3d transition metal single atoms as efficient oxygen reduction catalysts.

Carbon-based support anchored 3d transition metal (TM) single atom catalysts (SACs) have been widely considered as promising candidates for the oxygen reduction reaction (ORR), and their intrinsic activity is closely related to the geometric and electronic structures of the supports. T-graphene was predicted to have high conductivity and stability, so it may be also a promising support for loading SACs for electrocatalysis. Here, we systematically evaluate the ORR activity of T-graphene supported TM single atoms (TMN4-Tgra and TMC4-Tgra, TM = Sc-Zn) and their graphene supported counterparts (TMN4-Gra and TMC4-Gra). The TM(dxz)-O(px), TM(dyz)-O(py) and TM(dz2)-O(pz + s) orbital hybridizations between the active central metal and the *OH intermediate determine the ORR activity. Compared to graphene, T-graphene increases the d-band center (especially the ß-spin state) of single atoms and reduces the *OH adsorption strength, which thus improves the ORR activity of the catalysts located in the left leg of the ORR activity volcano plot. Interestingly, we found that for the catalysts with different TMs anchored on the same support, the adsorption strength of oxygen intermediates increases with the increase of the d-band center of the active site, while for the catalysts with the same metal anchored on different supports, the adsorption strength of oxygen intermediates weakens with the increase of the d-band center of the active site, which can serve as a d-band center dependence law on supports and active sites for designing ORR catalysts.

Strain Engineering of the NiTe/Ni2P Heterostructure to Boost the Oxygen Evolution Reaction.

Discovering highly efficient and stable non-precious metal catalysts for the oxygen evolution reaction (OER) is crucial for energy conversion in water splitting. However, preparing high-performance OER catalysts and elucidating the structural changes in the process are still challenging. Herein, we synthesize the NiTe/Ni2P heterostructure and demonstrate the strain engineering of NiTe/Ni2P via the lattice incompatibility between the phosphide and the telluride. The strain engineering of the NiTe/Ni2P heterostructure not only significantly boosts the OER activity but also effectively stabilizes the intrinsic structure of the catalyst after the OER process by using the in situ-produced metal salt as a protection layer. After the OER stability test, no oxyhydroxide phase is observed, and in situ Raman spectroscopy reveals that a voltage-dependent phase transition appears during the OER, which is different from most previously reported Ni-based catalysts, for which the generation of irreversible NiOOH occurs after the OER. Density functional theory calculations further reveal that the tensile strain of Ni2P will inhibit the presence of irreversible phase transitions of Ni2P into NiOOH due to the weak adsorption ability of the oxygen species caused by strain engineering. In short, this work opens a new gate for using strain nanotechnology to design high-performance OER catalysts.

High-Rate Organic Cathode Constructed by Iron-Hexaazatrinaphthalene Tricarboxylic Acid Coordination Polymer for Li-Ion Batteries.

The sluggish ion-transport in electrodes and low utilization of active materials are critical limitations of organic cathodes, which lead to the slow reaction dynamics and low specific capacity. In this study, the hierarchical tube is constructed by iron-hexaazatrinaphthalene tricarboxylic acid coordination polymer (Fe-HATNTA), using HATNTA as the self-engaged template to coordinate with Fe2+ ions. This Fe-HATNTA tube with hierarchical porous structure ensures the sufficient contact between electrolyte and active materials, shortens the diffusion distance, and provides more favorable transport pathways for ions. When employed as the cathode for rechargeable Li-ion batteries, Fe-HATNTA delivers a high specific capacity (244 mAh g-1 at 50 mA g-1 , 91% of theoretical capacity), excellent rate capability (128 mAh g-1 at 9 A g-1 ), and a long-term cycle life (73.9% retention over 3000 cycles at 5 A g-1 ). Moreover, the Li+ ions storage and conduction mechanisms are further disclosed by the ex situ and in situ characterizations, kinetic analyses, and theoretical calculations. This work is expected to boost further enthusiasm for developing the hierarchical structured metal-organic coordination polymers with superb ionic storage and transport as high-performance organic cathodes.