Magnetic fields promote electrocatalytic CO2 reduction via subtle modulations of magnetic moments and molecular bonding.

Introducing a magnetic-field gradient into an electrically driven chemical reaction is expected to give rise to intriguing research possibilities. In this work, we elaborate on the modes and mechanisms of electrocatalytic activity (from the perspective of alignment of magnetic moments) and selectivity (at the molecular level) for the CO2 reduction reaction in response to external magnetic fields. We establish a positive correlation between magnetic field strengths and apparent current densities. This correlation can be rationalized by the formation of longer-range ordering of magnetic moments and the resulting decrease in the scattering of conduction electrons and charge-transfer resistances as the field strength increases. Furthermore, aided by the magnetic-field-equipped operando infrared spectroscopy, we find that applied magnetic fields are capable of weakening the C-O bond strength of the key intermediate ∗COOH and elongating the C-O bond length, thereby increasing the faradaic efficiency for the electroreduction of CO2 to CO.

Gadolinium Changes the Local Electron Densities of Nickel 3d Orbitals for Efficient Electrocatalytic CO2 Reduction.

Generally, in terms of electrocatalytic CO2 reduction, single-atom catalysts show high selectivities yet low current densities whereas conventional nanoparticle catalysts exhibit relatively high current densities but low selectivities. This work combines the advantages of the two classes of catalysts by constructing a Ni-Gd-N-doped carbon black electrocatalyst within which NiI active sites are exposed outside the carbon layers and Ni nanoparticles are encapsulated inside the carbon layers. The Gd atoms can not only influence the local electron densities of Ni 3d orbitals, thus strengthening the electronic activity, but also tailor the sizes of the Ni nanoparticles, thereby minimizing the activity toward hydrogen evolution. Accordingly, this electrocatalyst yields both a high CO faradaic efficiency (97 %) and a large current density (308 mA cm-2 ), alongside an outstanding stability (100 h).

Ultrasonic synthesis of Mn-Ni-Fe tri-metallic oxide anchored on polymer-grafted conductive carbon for rechargeable zinc-air battery.

As a promising electrochemical energy device, a rechargeable zinc-air battery (RZAB) requires cost-effective cathode catalysts for oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). Some earth-abundant transition metal oxides have certain levels of bi-functional ORR/OER catalytic activities yet low electronic conductivities. The addition of high-electronic-conductivity material such as carbon black could result in another problem because there is low compatibility between metal oxide and carbon. In this work, polymer chains are ultrasonically prepared to act as binders to anchor metal-oxide active sites to porous domains of carbon black. The monomer N-isopropyl acrylamide is polymerized under ultrasonication instead of using conventional radical initiators which are dangerous and harmful. Reactive free radicals produced by ultrasonic irradiation can also help to form the Mn-Ni-Fe tri-metallic oxide. Thus, aided by the amide-type polymer as an adhesive, the tri-metallic oxide anchored on polymer-grafted carbon black prepared by ultrasonication possess a large number of metal-oxide active sites and hierarchical pores, contributing substantially to the enhanced ORR/OER electrocatalytic performance in the RZABs. Accordingly, this work provides interesting insight into the effective combination of inherently incompatible components for the fabrication of composite materials from an ultrasonic standpoint.

Boosting electrochemical performance of activated carbon by tuning effective pores and synergistic effects of active species.

Clean energy conversion/storage techniques have become increasingly significant because of the increasing energy consumption. Regarding practical applications like zinc-air batteries and supercapacitors, electrode materials are essential and often require both porous networks and active species to enhance their electrochemical performance. Nitrogen-doped porous carbon (NPC) is a kind of promising material, which provides efficient active sites and large surface areas for energy conversion/storage applications. However, rational modulation of properties for maximizing NPC performance is still a challenge. Herein, a promising NPC material derived from natural biomass is successfully synthesized by following a stepwise preparation method. Physisorption and X-ray photoelectron spectroscopy (XPS) analyses demonstrate both pore structures and nitrogen species of the NPC have been delicately tuned. The optimized sample NPC-800-m exhibits excellent performance in both oxygen reduction reaction (ORR) and three-electrode supercapacitor measurement. Moreover, the homemade zinc-air battery and symmetric supercapacitor assembled with NPC-800-m also display outstanding energy and power density as well as durable stability. Density functional theory (DFT) calculations further confirm the synergistic effects among graphitic, pyridinic and pyrrolic nitrogen. The existence of multispecies of nitrogen combined with the optimized pore structure is the key to the high electrochemical performance for NPC-800-m. This work not only provides feasible and green synthetic methodology but also offers original insights into the effective pores and the synergistic effects of different nitrogen species in the NPC materials.

Ultrasound-assisted transformation from waste biomass to efficient carbon-based metal-free pH-universal oxygen reduction reaction electrocatalysts.

Efficient carbon-based nitrogen-doped electrocatalysts derived from waste biomass are regarded as a promising alternative to noble metal catalysts for oxygen reduction reaction (ORR), which is crucial to fuel cell performance. Here, coconut palm leaves are employed as the carbon source and a series of nitrogen-doped porous carbons were prepared by virtue of a facile and mild ultrasound-assisted method. The obtained carbon material (ANDC-900-10) conveys excellent pH-universal catalytic activity with onset potentials (Eonset) of 1.01, 0.91 and 0.84 V vs. RHE, half-wave potentials (E1/2) of 0.87, 0.74 and 0.66 V vs. RHE and limiting current densities (JL) of 5.50, 5.45 and 4.97 mA cm-2 in alkaline, neutral and acidic electrolytes, respectively, prevailing over the commercial Pt/C catalyst and, what's more, ANDC-900-10 displays preeminent methanol crossover resistance and long-term stability in the broad pH range (0-13), thanks to its abundant hierarchical nanopores as well as effective nitrogen doping with high-density pyridinic-N and graphitic-N. This work provides sonochemical insight for underpinning the eco-friendly approach to rationally designing versatile metal-free carbon-based catalysts toward the ORR at various pH levels.

Template-free preparation of anthracite-based nitrogen-doped porous carbons for high-performance supercapacitors and efficient electrocatalysts for the oxygen reduction reaction.

The conversion of coal into high-performance electrochemical energy materials, exemplified by electrodes and electrocatalysts for supercapacitors and fuel cells, is currently crucial to the advancement of high value-added, clean and non-fuel utilization of coal resources. In this work, anthracite-based nitrogen-doped porous carbon (ANPC) materials with well-defined pore architectures and adjustable nitrogen concentrations were prepared without any template: ANPC-1 by a one-step activation/doping process and ANPC-2 by a two-step process. The specific capacitance value of the ANPC-1 materials could attain a maximum of 346.0 F g-1 at the current density of 0.5 A g-1 in 6 M KOH. Supercapacitors composed of the ANPC-1 electrodes were able to achieve high energy densities up to 10.3 W h kg-1 and 20.8 W h kg-1, together with good charge/discharge stabilities of 95.4% and 91.3% after 5000 cycles, in KOH and Na2SO4 aqueous electrolytes, respectively. The ANPC-2 materials are more associated with the oxygen reduction reaction (ORR): one possessed a comparable ORR electrocatalytic activity to the commercial JM Pt/C (20% Pt) catalyst, and, moreover, its onset potential (0.96 V vs. RHE), half-wave potential (0.85 V vs. RHE), catalyst durability (95.9% activity retained after 40 000 s) and methanol tolerance were all superior to the benchmark electrocatalyst. This study provides a feasible route to rational design of coal-based multifunctional materials towards electrochemical energy storage and conversion.

An ultrasound-assisted approach to bio-derived nanoporous carbons: disclosing a linear relationship between effective micropores and capacitance.

Ultrasound irradiation is a technique that can induce acoustic cavitation in liquids, leading to a highly interactive mixture of reactants. In pursuit of high-performance and cost-effective supercapacitor electrodes, pore size distributions of carbonaceous materials should be carefully designed. Herein, fruit skins (mango, pitaya and watermelon) are employed as carbon precursors to prepare nanoporous carbons by the ultrasound-assisted method. Large BET specific surface areas of the as-prepared carbons (2700-3000 m2 g-1) are reproducible with pore diameters being concentrated at about 0.8 nm. Among a suite of the bio-derived nanoporous carbons, one reaches a maximum specific capacitance of up to 493 F g-1 (at 0.5 A g-1 in 6 M KOH) in the three-electrode system and achieves high energy densities of 27.5 W h kg-1 (at 180 W kg-1 in 1 M Na2SO4) and 10.9 W h kg-1 (at 100 W kg-1 in 6 M KOH) in the two-electrode system. After 5000 continuous charge/discharge cycles, the capacitances maintain 108% in 1 M Na2SO4 and 98% in 6 M KOH, exhibiting long working stability. Moreover, such high capacitive performance can be attributed to the optimization of surface areas and pore volumes of the effective micropores (referred to as 0.7-2 nm sized pores). Notably, specific capacitances have been found linearly correlated with surface areas and pore volumes of the effective micropores rather than those of any other sized pore (i.e., <0.7, 2-50 and 0.5-50 nm). Consequently, the fit of electrolyte ions into micropore frameworks should be an important consideration for the rational design of nanopore structures in terms of supercapacitor electrodes.

Harnessing inherently hierarchical microstructures of plant biomass to construct three-dimensional nanoporous nitrogen-doped carbons as efficient and durable oxygen reduction electrocatalysts.

Exploiting the natural structures of plants to prepare high-performance carbon-based electrocatalysts is highly desirable. Herein, the inherently hierarchical microstructures of Euphorbia tirucalli (E. tirucalli) are employed to construct three-dimensional nanoporous nitrogen-doped carbons that act as efficient and durable electrocatalysts towards the oxygen reduction reaction (ORR). During the preparation process, agar is used in order to reduce the dissipation of nitrogen and to protect the fine structures of E. tirucalli. The as-prepared ORR catalyst, with a high density of pyridinic and graphitic nitrogens, presents a high catalytic activity (onset potential of 0.97 V vs. RHE, half-wave potential of 0.82 V vs. RHE, limiting current density of 5.64 mA cm-2 and Tafel slope of 59 mV dec-1), four-electron pathway, low peroxide yield, long-term stability (current retention of 95.3% after 50 000 s) and strong methanol tolerance in 0.1 M KOH, all superior to the benchmark 20% Pt/C commercial catalyst. This work demonstrates an effective method for the utilization of inherently hierarchical microstructures of plant biomass to make efficient and durable carbon-based metal-free ORR electrocatalysts.