A molecular [Ru(bda)]-type(bda = 2,2’-bipyridine-6,6’-dicarboxylate) water oxidation catalyst with 4-vinylpyridine as the axial ligand(Complex 1) was immobilized or co-immobilized with 1-(trifluoromethyl)-4-vinylben...A molecular [Ru(bda)]-type(bda = 2,2’-bipyridine-6,6’-dicarboxylate) water oxidation catalyst with 4-vinylpyridine as the axial ligand(Complex 1) was immobilized or co-immobilized with 1-(trifluoromethyl)-4-vinylbenzene(3 F) or styrene(St) blocking units on the surface of glassy carbon(GC) electrodes by electrochemical polymerization, in order to prepare the corresponding poly-1@GC, poly-1+P3 F@GC, and poly-1+PSt@GC functional electrodes. Kinetic measurements of the electrode surface reaction revealed that [Ru(bda)] triggers the O–O bond formation via(1) the radical coupling interaction between the two metallo-oxyl radicals(I2 M) in the homo-coupling polymer(poly-1), and(2) the water nucleophilic attack(WNA) pathway in poly-1+P3 F and poly-1+PSt copolymers. The comparison of the three electrodes revealed that the second coordination sphere of the water oxidation catalysts plays vital roles in stabilizing their reaction intermediates, tuning the O–O bond formation pathways and improving the water oxidation reaction kinetics without changing the first coordination structures.展开更多
We report herein a Re-based tricarbonyl catalyst[fac-Re(L1)(CO)_(3)Cl](Re1)bearing a spiro center and a phenol group as a local proton source in the second coordination sphere.Due to the large steric spiro group,dimer...We report herein a Re-based tricarbonyl catalyst[fac-Re(L1)(CO)_(3)Cl](Re1)bearing a spiro center and a phenol group as a local proton source in the second coordination sphere.Due to the large steric spiro group,dimerization of one-electron reduced species was completely eliminated,improving the stability of Re1.Simultaneously,the phenol group in the second coordination sphere improves the formation of an H-bonding chain that promotes the protonation of C0_(2) reduction intermediates,boosting the electrocatalytic C0_(2) reduction activity of Re1.Mechanistic studies reveal that the doubly reduced complex Re1b is active for C0_(2) addition.展开更多
The lack of efficient and low-cost catalysts hinders the large-scale application of electrolytic water splitting.High-entropy oxides(HEOs)offer unique structures and promising properties for oxygen evolution reaction(...The lack of efficient and low-cost catalysts hinders the large-scale application of electrolytic water splitting.High-entropy oxides(HEOs)offer unique structures and promising properties for oxygen evolution reaction(OER)but are often synthesized via high-temperature methods,resulting in microscale particles with low active site exposure.HEO sub-1 nm nanosheets(SNSs)are synthesized using a cluster-nuclei co-assembly strategy with the introduction of phosphomolybdic acid(PMA)clusters.Molecular dynamics simulation results demonstrate that the PMA clusters act as linkers,facilitating the co-assembly of multimetal oxides into stable and ordered nanosheets via noncovalent interactions.Owing to the sub-nanoscale structure and precise elemental regulation,these SNSs demonstrate enhanced performance in OER.Among them,HEO-PMA SNSs demonstrated superior performance,achieving an overpotential of 229 mV at 10 mA cm^(-2)and exceptional long-term stability that lasted for over 1000 h at a large current density of 250 mA cm^(-2).Density functional theory calculations also demonstrate that the synergistic effect of multiple metals can significantly enhance the OER process.Composition engineering and sub-1 nm structural design in HEOs provide a promising strategy to enhance catalyst stability,addressing challenges related to low intrinsic activity,scarce active sites,and long-term durability in the OER process.展开更多
A disubstituted quaterpyridine based cobalt complex non‐covalently tethered to multiwalled carbon nanotube(MWCNT)substrate,forming a hybrid catalyst,Co‐qpyCOOH/CNT,catalyzed the conversion of CO_(2) to CO under aque...A disubstituted quaterpyridine based cobalt complex non‐covalently tethered to multiwalled carbon nanotube(MWCNT)substrate,forming a hybrid catalyst,Co‐qpyCOOH/CNT,catalyzed the conversion of CO_(2) to CO under aqueous conditions.At an optimal and uniform loading,it exhibited remarkable catalytic activity,near‐exclusive selectivity,and high stability towards the formation of CO.At a mere cathodic potential of−0.65 V versus RHE(η=0.54 V),it achieved a high partial current density of−6.7 mA/cm^(2) and a F.E.CO=100%.In addition,with 20 h of stable operation,hydrogen evolution remained practically undetected.Its hybrid structure due to noncovalent immobilization on MWCNT imparted the intrinsic activity and much‐needed stability in performance whereas‒COOH groups may stabilize the intermediates by acting as H‐bond donors,promoting catalytic activity.Tethering to a conductive solid substrate and tuning of the second sphere of coordination played an important role in its performance to achieve desired reduction product with high selectivity and activity.展开更多
文摘A molecular [Ru(bda)]-type(bda = 2,2’-bipyridine-6,6’-dicarboxylate) water oxidation catalyst with 4-vinylpyridine as the axial ligand(Complex 1) was immobilized or co-immobilized with 1-(trifluoromethyl)-4-vinylbenzene(3 F) or styrene(St) blocking units on the surface of glassy carbon(GC) electrodes by electrochemical polymerization, in order to prepare the corresponding poly-1@GC, poly-1+P3 F@GC, and poly-1+PSt@GC functional electrodes. Kinetic measurements of the electrode surface reaction revealed that [Ru(bda)] triggers the O–O bond formation via(1) the radical coupling interaction between the two metallo-oxyl radicals(I2 M) in the homo-coupling polymer(poly-1), and(2) the water nucleophilic attack(WNA) pathway in poly-1+P3 F and poly-1+PSt copolymers. The comparison of the three electrodes revealed that the second coordination sphere of the water oxidation catalysts plays vital roles in stabilizing their reaction intermediates, tuning the O–O bond formation pathways and improving the water oxidation reaction kinetics without changing the first coordination structures.
基金the National Natural Science Foundation of China(No.21771098)the Shenzhen R&D Fund(No.KQ.TD20180411143418361)+1 种基金the Shenzhen Clean Energy Research Institute(No.CERI-KY-2019-003)the Guangdong Provincial Key Laboratory of Energy Materials for Electric Power(No.2018B030322001).
文摘We report herein a Re-based tricarbonyl catalyst[fac-Re(L1)(CO)_(3)Cl](Re1)bearing a spiro center and a phenol group as a local proton source in the second coordination sphere.Due to the large steric spiro group,dimerization of one-electron reduced species was completely eliminated,improving the stability of Re1.Simultaneously,the phenol group in the second coordination sphere improves the formation of an H-bonding chain that promotes the protonation of C0_(2) reduction intermediates,boosting the electrocatalytic C0_(2) reduction activity of Re1.Mechanistic studies reveal that the doubly reduced complex Re1b is active for C0_(2) addition.
基金supported by the Hundred Talents Programs in the Chinese Academy of Sciencesthe Ningbo Yongjiang Talent Introduction Program(2021A-111-G)+2 种基金the Ningbo S&T Innovation 2025 Major Special Program(2022Z205)the Kunpeng Plan of Zhejiang Provincethe Ningbo Top Talent Program。
文摘The lack of efficient and low-cost catalysts hinders the large-scale application of electrolytic water splitting.High-entropy oxides(HEOs)offer unique structures and promising properties for oxygen evolution reaction(OER)but are often synthesized via high-temperature methods,resulting in microscale particles with low active site exposure.HEO sub-1 nm nanosheets(SNSs)are synthesized using a cluster-nuclei co-assembly strategy with the introduction of phosphomolybdic acid(PMA)clusters.Molecular dynamics simulation results demonstrate that the PMA clusters act as linkers,facilitating the co-assembly of multimetal oxides into stable and ordered nanosheets via noncovalent interactions.Owing to the sub-nanoscale structure and precise elemental regulation,these SNSs demonstrate enhanced performance in OER.Among them,HEO-PMA SNSs demonstrated superior performance,achieving an overpotential of 229 mV at 10 mA cm^(-2)and exceptional long-term stability that lasted for over 1000 h at a large current density of 250 mA cm^(-2).Density functional theory calculations also demonstrate that the synergistic effect of multiple metals can significantly enhance the OER process.Composition engineering and sub-1 nm structural design in HEOs provide a promising strategy to enhance catalyst stability,addressing challenges related to low intrinsic activity,scarce active sites,and long-term durability in the OER process.
基金Zhejiang Provincial Natural Science Foundation of China,Grant/Award Number:LZ20B030001Agency for Science,Technology,and Research(A*STAR),Singapore,Grant/Award Number:AME Individual Research Grant(Grant A1983c0026)+1 种基金Campus for Research Excellence and Technological Enterprise(CREATE)program,National Research Foundation(NRF),Prime Minister's Office,SingaporeNational Natural Science Foundation of China,Grant/Award Numbers:21972106,51872209。
文摘A disubstituted quaterpyridine based cobalt complex non‐covalently tethered to multiwalled carbon nanotube(MWCNT)substrate,forming a hybrid catalyst,Co‐qpyCOOH/CNT,catalyzed the conversion of CO_(2) to CO under aqueous conditions.At an optimal and uniform loading,it exhibited remarkable catalytic activity,near‐exclusive selectivity,and high stability towards the formation of CO.At a mere cathodic potential of−0.65 V versus RHE(η=0.54 V),it achieved a high partial current density of−6.7 mA/cm^(2) and a F.E.CO=100%.In addition,with 20 h of stable operation,hydrogen evolution remained practically undetected.Its hybrid structure due to noncovalent immobilization on MWCNT imparted the intrinsic activity and much‐needed stability in performance whereas‒COOH groups may stabilize the intermediates by acting as H‐bond donors,promoting catalytic activity.Tethering to a conductive solid substrate and tuning of the second sphere of coordination played an important role in its performance to achieve desired reduction product with high selectivity and activity.
