Electrocatalytic Systems Research Articles

Sustainable application of electrocatalytic and photo-electrocatalytic oxidation systems for water and wastewater treatment: a review.

Wastewater treatment and reuse have risen as a solution to the water crisis plaguing the world. Global warming-induced climate change, population explosion and fast depletion of groundwater resources are going to exacerbate the present global water problems for the forthcoming future. In this scenario, advanced electrochemical oxidation process (EAOP) utilising electrocatalytic (EC) and photoelectrocatalytic (PEC) technologies have caught hold of the interest of the scientific community. The interest stems from the global water management plans to scale down centralised water and wastewater treatment systems to decentralised and semicentralised treatment systems for better usage efficiency and less resource wastage. In an age of rising water pollution caused by contaminants of emerging concern (CECs), EC and PEC systems were found to be capable of optimal mineralisation of these pollutants rendering them environmentally benign. The present review treads into the conventional electrochemical treatment systems to identify their drawbacks and analyses the scope of the EC and PEC to mitigate them. Probable electrode materials, potential catalysts and optimal operational conditions for such applications were also examined. The review also discusses the possible retrospective application of EC and PEC as point-of-use and point-of-entry treatment systems during the transition from conventional centralised systems to decentralised and semi-centralised water and wastewater treatment systems.

Dimensional engineering of covalent organic frameworks derived carbons for electrocatalytic carbon dioxide reduction

AbstractCovalent organic frameworks (COFs) have been developed as the precursors to construct porous carbons for electrocatalytic systems. However, the influences of carbon dimensions on the catalytic performance are still underexplored. In this work, we have first constructed COF‐derived carbons by template‐synthesis strategy in different dimensions to catalyze the carbon dioxide reduction (CO2RR). By using different templates, the one‐dimensional (1D), two‐dimensional (2D), and three‐dimensional (3D) COF‐derived carbons have been employed to anchor Co‐porphyrin to form the Co‐N5 sites to catalyze CO2RR. The 1D catalyst templated by carbon nano tubes presents high binding ability of CO2, more defective sites, and higher electronic conductivity, resulting in a higher catalytic activity for CO2 and selectivity of CO than 2D and 3D carbon‐based catalysts. The 1D catalyst delivers the turnover frequency values of 1150 h−1 and the FECO of 94.5% at 0.7 V versus RHE, which is significantly better than those of 2D and 3D carbon‐based catalysts.

Applications of electro-catalysis municipal wastewater treatment

In the context of developing a more livable environment, people are paying more attention to the pollution problem. As the consumption of water resources increases, water pollution is one of the most serious problems people need to pay attention to the most. However, traditional methods cannot meet the requirements of treating wastewater while recovering resources. In this review, the application of electrocatalytic technology in municipal wastewater treatment is discussed. Specifically, the comparison between electrocatalysis and traditional methods is shown in this review. Various literatures on different types of materials of electrodes are included. Besides, two different types of electrodes and mechanisms of electrocatalysis and their application in multiple types of wastewater are also summarized. This review aims to arouse peoples attention to the wastewater problem and explore the further application of electrocatalytic technology in the future in order to rationally design new electrocatalytic systems for the recovery of energy and resources.

Electrocatalytic Systems for NOx Valorization in Organonitrogen Synthesis.

Inorganic nitrogen oxide (NOx ) species, such as NO, NO2 , NO3 - , NO2 - generated from the decomposition of organic matters, volcanic eruptions and lightning activated nitrogen, play important roles in the nitrogen cycle system and exploring the origin of life. Meanwhile, excessive emission of NOx gases and residues from industry and transportation causes troubling problems to the environment and human health. How to efficiently handle these wastes is a global problem. In response to the growing demand for sustainability, scientists are actively pursuing sustainable electrochemical technologies powered by renewable energy sources and efficient utilization of hydrogen energy to convert NOx species into high-value organonitrogen chemicals. In this minireview, recent advances of electrocatalytic systems for NOx species valorization in organonitrogen synthesis are classified and described, such as amino acids, amide, urea, oximes, nitrile etc., that have been widely applied in medicine, life science and agriculture. Additionally, the current challenges including multiple side reactions and complicated paths, viable solutions along with future directions ahead in this field are also proposed. The coupling electrocatalytic systems provide a green mode for fixing nitrogen cycle bacteria and bring enlightenment to human sustainable development.

Electrocatalytic Systems for NOx Valorization in Organonitrogen Synthesis

AbstractInorganic nitrogen oxide (NOx) species, such as NO, NO2, NO3−, NO2− generated from the decomposition of organic matters, volcanic eruptions and lightning activated nitrogen, play important roles in the nitrogen cycle system and exploring the origin of life. Meanwhile, excessive emission of NOx gases and residues from industry and transportation causes troubling problems to the environment and human health. How to efficiently handle these wastes is a global problem. In response to the growing demand for sustainability, scientists are actively pursuing sustainable electrochemical technologies powered by renewable energy sources and efficient utilization of hydrogen energy to convert NOx species into high‐value organonitrogen chemicals. In this minireview, recent advances of electrocatalytic systems for NOx species valorization in organonitrogen synthesis are classified and described, such as amino acids, amide, urea, oximes, nitrile etc., that have been widely applied in medicine, life science and agriculture. Additionally, the current challenges including multiple side reactions and complicated paths, viable solutions along with future directions ahead in this field are also proposed. The coupling electrocatalytic systems provide a green mode for fixing nitrogen cycle bacteria and bring enlightenment to human sustainable development.

Highly-efficient natural gas desulfurization and simultaneous H2O2 synthesis based on the electrochemical coupling reaction strategy

Hydrogen sulfide (H2S) generated by natural gas exploitation is a dangerous and harmful gas that needs to be purified. Electrochemical Natural Gas Desulfurization offers a promising way for H2S purification and resource utilization in ambient conditions. However, poor energy efficiency and low resource value limit the prospective application in the industry. Herein, we propose a gas-liquid flow electrocatalysis system that couples H2S oxidation and O2 reduction processes to effectively recover sulfur and H2O2 with low energy consumption. Gas diffusion and mass transfer are accelerated by gas-liquid flow cells, which also significantly decrease the resistance. Besides, I-/I3- redox pairs promote selective H2S oxidation while inhibiting water decomposition, resulting in a 56% reduction in oxidation potential. Moreover, the surface proton concentration is elevated by employing a modified carbon gas diffusion electrode (GDE), which assists to maintains a high H2O2 faradic efficiency. The system is able to operate at a high current density of 102 mA/cm2 at an Ecell voltage of 3.5 V, yielding S and H2O2 at rates of 60 mg cm−2 h−1 and 50 mg cm−2 h−1 respectively. A techno-economic model forecasts the effects of system efficiency and energy prices on operational costs and illustrates potential routes to a plant-gate levelized application in the petrochemical industry.

Toward a comprehensive hypothesis of oxygen-evolution reaction in the presence of iron and gold

This study investigates the effects of Fe on the oxygen-evolution reaction (OER) in the presence of Au. Two distinct areas of OER were identified: the first associated with Fe sites at low overpotential (∼330 mV), and the second with Au sites at high overpotential (∼870 mV). Various factors such as surface Fe concentration, electrochemical method, scan rate, potential range, concentration, method of adding K2FeO4, nature of Fe, and temperature were varied to observe diverse behaviors during OER for FeOxHy/Au. Trace amounts of Fe ions had a significant impact on OER, reaching a saturation point where the activity did not increase further. Strong electronic interaction between Fe and Au ions was indicated by X-ray photoelectron spectroscopy (XPS) and electron paramagnetic resonance (EPR) analyses. In situ visible spectroscopy confirmed the formation of FeO42− during OER. In situ Mössbauer and surface-enhancedRamanspectroscopy (SERS) analyses suggest the involvement of Fe-based species as intermediates during the rate-determining step of OER. A lattice OER mechanism based on FeOxHy was proposed for operation at low overpotentials. Density functional theory (DFT) calculations revealed that Fe oxide, Fe-oxide clusters, and Fe doping on the Au foil exhibited different activities and stabilities during OER. The study provides insights into the interplay between Fe and Au in OER, advancing the understanding of OER mechanisms and offering implications for the design of efficient electrocatalytic systems.

Electro-inductive Effect Dominates Vibrational Frequency Shifts of Conjugated Probes on Gold Electrodes.

Interfacial electric fields play a critical role in electrocatalysis and are often characterized by using vibrational probes attached to an electrode surface. Understanding the physical principles dictating the impact of the applied electrode potential on the vibrational probe frequency is important. Herein, a comparative study is performed for two molecular probes attached to a gold electrode. Both probes contain a nitrile (CN) group, but 4-mercaptobenzonitrile (4-MBN) exhibits continuous conjugation from the electrode through the nitrile group, whereas this conjugation is interrupted for 2-(4-mercaptophenyl)acetonitrile (4-MPCN). Periodic density functional theory calculations predict that the CN vibrational frequency shift of the 4-MBN system is dominated by induction, which is a through-bond polarization effect, leading to a strong potential dependence that does not depend significantly on the orientation of the CN bond relative to the surface. In contrast, the CN vibrational frequency shift of the 4-MPCN system is influenced less by induction and more by through-space electric field effects, leading to a weaker potential dependence and a greater orientation dependence. These theoretical predictions were confirmed by surface-enhanced Raman spectroscopy experiments. Balancing through-bond and through-space electrostatic effects may assist in the fundamental understanding and design of electrocatalytic systems.

Size-controlled Co/CoO heterogeneous nanoparticles confined in N-doped mesoporous carbon for efficient oxygen reduction in zinc-air batteries

The size of metal compound particles and interface electronic structure of heterojunctions in a matrix greatly affect oxygen reduction performance in zinc-air batteries. However, it is still a big challenge to precisely control or regulate the size of these metal compound particles and the heterojunction structure. Herein, cobalt complexes with different-sized ligands are chosen as cobalt resources and adsorbed onto a mesoporous carbon, after which they are coated with polydopamine and calcined. Under the confinement effect of mesopores and the isolation effect of ligands and dopamine, the as-obtained Co/CoO heterogeneous nanoparticles are restricted to nano-size and uniformly dispersed in N-doped carbon (NC). The sizes of Co/CoO are estimated to be 39.7, 24.9 and 15.6 nm with increased CoO contents, corresponding to the adopted cobalt precursors of Co(OAc)2, Co(acac)2 and Co(acac)3, respectively. The smallest Co/CoO/NC-S shows excellent catalytic activity for oxygen reduction reaction, with a half-wave potential of 0.82 V vs. RHE and a limiting current density of 4.59 mA cm−2. When applied to the cathode of zinc-air battery, a high peak power density of 131.9 mW cm−2 is achieved, which surpasses that of the battery powered by Pt/C. The excellent performance can be attributed to the formation of heterogeneous structures between Co and CoO, the smaller Co/CoO nanoparticles, and N-doped mesoporous carbon with effective charge/mass transport. This work provides an effective way to regulate the size and phase contents of heterogeneous particles in mesoporous carbon, which is highly valuable in electrocatalytic systems.

Aminosilanized Interface Promotes Electrochemically Stable Carbon Nitride Films with Fewer Trap States on FTO for (Photo)electrochemical Systems.

We have demonstrated the direct growth of a CNx layer on a plasma-cleaned and aminosilanized F-doped SnO2 (FTO) electrode to study the CNx|FTO interface that is critical for (photo)electrocatalytic systems. The (3-aminopropyl)triethoxysilane (APTES) was chosen as a bifunctional organosilane, with the amino end incorporating into CNx and the silane end connecting to the hydroxylated FTO surface. Plasma cleaning and aminosilanization resulted in a highly hydrophilic surface, which leads to better contact of melted thiourea to the aminosilanized FTO (p-FTONH2) during CNx polymer condensation, thus generating a thinner and more compact CNx layer. The modification at the interface was shown to influence the CNx growth on length scales of tens of micrometers. We grew CNx thin films on p-FTONH2 (CNx/p-FTONH2) and nonaminosilanized p-FTO (CNx/p-FTO). CNx/p-FTONH2 had a smaller density of trap states and passed 2.4 times the charges before failure compared to CNx/p-FTO. Additionally, a 40% decrease in interfacial charge transfer resistance at the CNx|electrolyte interface was measured for CNx/p-FTONH2 compared to CNx/p-FTO under -0.5 V vs RHE in 0.1 M Na2SO4. Furthermore, with the CNx surface coated with a Pt cocatalyst, Pt/CNx/p-FTONH2 exhibited faster hydrogen evolution rates and larger current densities than Pt/CNx/p-FTO. The highest Faraday efficiency toward electrochemical hydrogen evolution (FEH2) in 0.1 M Na2SO4 (pH = 7) was 46.1%, 37.3%, 57.7%, and 70.5% for Pt/CNx/p-FTONH2, Pt/CNx/p-FTO, CNx/p-FTONH2, and CNx/p-FTO, respectively. The increase in hydrogen evolution rate did not follow the magnitude of the current density change, indicating electrochemical processes other than proton reduction. Overall, we have carefully investigated the CNx|FTO interface and suggested potential solutions to make CNx films better (photo)electrodes for (photo)electrochemical systems.

Exploring spin states by hybrid functional methods to define correct trends in electrocatalytic activity of SACs embedded in N-doped graphene

Embedding transition metal atoms in graphene is a promising strategy to make it an effective electrocatalyst for the oxygen evolution (OER) and reduction (ORR) reactions, which are crucial processes for the success of the energy transition. In this regard, theoretical investigations can be valuable complementary tools to experimental work, but only if they are able to adequately describe the system under examination. Transition metal atoms trapped in graphene pose serious challenges due to the presence of strongly correlated d-electrons, which can lead to complex spin configurations to be explored. In this work, by hybrid density functional theory (DFT) calculations we investigated several first-row transition metal atoms embedded in N-doped graphene as potential electrocatalysts for the OER and ORR. A detailed spin-dependent search has been performed to define the lowest energy spin state configurations for all intermediates along the associative path, finding Ni and Fe as the most promising systems for the OER and ORR, based on overpotential values (η) of 0.58 V and 0.52 V, respectively. Interestingly, if the study is limited to low-spin configurations, the resulting overpotential values differ within the range of 0.5 V, changing the order of activity between the various electrocatalytic systems. The most striking case is that of Fe, where according to the low-spin state reaction path it would suggest this to be the worst electrocatalyst for ORR. Thus, this work conveys a very important message and general warning to the community on trusting only data that come from a full spin optimization.

Noncovalent composites of meso-substituted A2B2-porphyrins and carbon nanotubes for enhanced electrocatalytic oxygen reduction

Exploring highly active oxygen reduction electrocatalysts with low precious metals content is imperative but remains a considerable challenge. Herein, a series of heterobimetallic multi-walled carbon nanotubes (MWCNTs) electrocatalysts based on metal complexes are presented. These electrocatalysts feature diverse transition metals (M=Mn, Fe, Co, Ni) 5,15-bromophenyl-10, 20-methoxyphenyl porphyrin (MBMP) and tetrakis(triphenylphosphine)palladium (0) (Pd[P(Ph3)4]) anchored non-covalently on its surface. The resulting NiBMP-based MWCNTs with Pd[P(Ph3)4] (PdNiN4/MWCNTs) display outstanding electrocatalytic oxygen reduction activity (onset potential, 0.941 V; half wave potential, 0.830 V) and robust long-term durability in alkaline electrolyte. While in neutral condition, the MnBMP-based MWCNTs with Pd[P(Ph3)4] (PdMnN4/MWCNTs) are the most active heterobimetallic ORR catalyst and produce ultra-low concentration hydrogen peroxide (H2O2 yield, 1.2%–1.3%). Synergistically tuning the ORR electrocatalytic activity and electron transfer pathway is achieved by the formation of NiBMP/MnBMP-Pd[P(Ph3)4] active sites. This work indicates such metalloporphyrin-Pd[P(Ph3)4] active sites on MWCNTs have significantly positive influence on electrocatalytic ORR systems and provides facile and mild strategy for designing highly efficient ORR electrocatalysts with ultra-low loading precious metal.

A dual-enzyme microreactor based on encapsulation and covalent bond for enzymatic electrocatalytic CO2 reduction

Enzymatic reduction of CO2 into high-value chemicals has become an emerging technology attributed to its high selectivity and catalytic efficiency under mild conditions. While, the low solubility of CO2 at room temperature, the expensive cofactors and the poor stability of free enzyme limit the application potential. To solve these problems, we used organic microcapsules together with MOF to protect formate dehydrogenase (FDH) by encapsulation and carbonic anhydrase (CA) by covalent bond with high CO2 capture ability to construct a dual-enzyme microreactor. Besides, the additional mesopores of the microreactor can ensure the efficient internal diffusion of the substrate and product. Electron mediator was used to enhance electrocatalytic NADH regeneration to efficiently reduce CO2 to formate in the enzyme electrocatalysis system. After optimization, the highest yield of formate in the electrocatalytic CO2 reduction system by the dual enzyme microreactor was 2.917 mM with a generation rate of 1.296 × 104 μmol gcat-1h−1, which was 8.9 times higher than free enzyme.

Efficient defluorination of perfluorooctanoic acid enabled by single-atom Cu/reduced graphene oxide electrocatalytic anode and peroxymonosulfate activation

In this study, an electrocatalytic system using reduced graphene oxide supported single-atom copper (SA-Cu/rGO) anode was constructed for perfluorooctanoic acid (PFOA) defluorination. The successful doping of SA-Cu elevated the oxygen evolution potential and electrochemical active surface area of the anode and provided high electrocatalytic properties. Under optimum initial conditions with a peroxymonosulfate (PMS) concentration of 10 mM, a current density of 15 mA·cm−2, and an unadjusted pH of 7.75, the SA-Cu/rGO system achieved 98.8% removal ratio, 92.5% defluorination, and 94.4% mineralization of 20 mg·L-1 PFOA in 120 min. Kinetic studies indicate PFOA degradation following a pseudo-first-order model, with a rate constant of 4.7 × 10−2 min−1. The presence of PMS in the electrocatalytic system significantly improved the degradation rate and defluorination ratio. Radical trapping and quenching experiments confirmed that both ·OH and ·SO4- radicals contributed to PFOA degradation, with ·SO4- playing a more important role in defluorination. The system show high flexibility in initial PFOA concentrations (0.2–20 mg·L−1) and environmental pH values (3.0–10.0), as well as good durability. The electrocatalytic degradation mechanism of PFOA was proposed through determination of intermediates and density functional theory (DFT) calculation. The total short-chain perfluorocarboxylic acids (PFCAs) intermediates generated throughout the degradation were far from sufficient recovery of the PFOA loss, indicating that apart from the ·OH mediated decarboxylation-hydroxylation-elimination-hydrolysis (DHEH) pathway, the ·SO4- mediated decarboxylation-hydroxylation-oxidation-decarbonyl fluoride (DHOD) pathway may play a significant role in the near-complete defluorination and mineralization of PFOA. Moreover, DFT calculations suggest that the DHOD pathway is energetically favorable over DHEH. This study provides a further understanding of the defluorination mechanism of PFOA in electrocatalytic systems and demonstrates that electrochemical degradation with single-atom copper catalyst is an promising method for PFOA remediation in aqueous environment.

Role of non-covalent interactions in 2,5-di-Me-pyrazine-di-N-oxide - tertiary butyl alcohol - single-walled and multi-walled carbon nanotubes electrocatalytic systems

Oxidation of tert-butyl alcohol (tert-BuOH, Me3COH), a compound with a high C-H bond breaking energy in the absence of precious metals or their oxides as catalysts and using metal-free electrodes, is an inexpensive process and is of interest for practical applications in electrocatalysis and sensors. In this work, electrocatalytic systems 2,5-di-Me-pyrazine-di-N-oxide (Pyr1) - tert-BuOH – single - walled (SWCNT) and multi-walled (MWCNT) carbon nanotube paper electrodes in 0.1 M Bu4NClO4 solution in acetonitrile (MeCN) were studied by the methods of cyclic voltammetry, quantum chemical modeling and electron paramagnetic resonance (EPR) electrolysis. Calculaition of energies of non-covalent interactions between the components of the electrocatalytic system in complexes Me3COH*Me3COH, Me3COH*MeCN, Pyr1*Me3COH and the adsorption energy of Me3COH and complexes of Pyr1*Bu4NClO4, Pyr1*Me3COH, Pyr1*MeCN and Me3COH *Bu4NClO4 on CNTs surface using a cluster model describing the surface of conducting carbon nanotubes (10, 10) was performed. The study made it possible to reveal the regularities characteristic of aromatic-di-N-oxide – CNT electrocatalytic systems and to propose a mechanism of tert-BuOH oxidation in the presence of electrochemically generated radical cation Pyr1. The data will be useful at using CNT electrodes in electrocatalytic processes, as well as aromatic di-N-oxide-CNT catalytic systems in electrocatalysis and sensors.

Single-atom Zr embedded Ti4O7 anode coupling with hierarchical CuFe2O4 particle electrodes toward efficient electrooxidation of actual pharmaceutical wastewater

Electrocatalytic oxidation is commonly restricted by low degradation efficiency, slow mass transfer, and high energy consumption. Herein, a synergetic electrocatalysis system was developed for removal of various drugs, i.e., atenolol, florfenicol, and diclofenac sodium, as well as actual pharmaceutical wastewater, where the newly-designed single-atom Zr embedded Ti4O7 (Zr/Ti4O7) and hierarchical CuFe2O4 (CFO) microspheres were used as anode and microelectrodes, respectively. In the optimal reaction system, the degradation efficiencies of 40 mg L–1 atenolol, florfenicol, and diclofenac sodium could achieve up to 98.8%, 93.4%, and 85.5% in 120 min with 0.1 g L–1 CFO at current density of 25 mA cm–2. More importantly, in the flow-through reactor, the electrooxidation lasting for 150 min could reduce the COD of actual pharmaceutical wastewater from 432 to 88.6 mg L−1, with a lower energy consumption (25.67 kWh/m3). Meanwhile, the electrooxidation system maintained superior stability and environmental adaptability. DFT theory calculations revealed that the excellent performance of this electrooxidation system could be ascribed to the striking features of the reduced reaction energy barrier by single-atom Zr loading and abundant oxygen vacancies on the Zr/Ti4O7 surface. Moreover, the characterization and experimental results demonstrated that the CFO unique hierarchical structure and synergistic effect between electrodes were also the important factors that could improve the system performance. The findings shed light on the single-atom material design for boosting electrochemical oxidation performance.

Modulating the Density of Catalytic Sites in Multiple-Component Covalent Organic Frameworks for Electrocatalytic Carbon Dioxide Reduction.

It is generally assumed that the more metal atoms in covalent organic frameworks (COFs) contribute to higher activity toward electrocatalytic carbon dioxide reduction (CO2RR) and hindered us in exploring the correlation between the density of catalytic sites and catalytic performances. Herein, we have constructed quantitative density of catalytic sites in multiple COFs for CO2RR, in which the contents of phthalocyanine (H2Pc) and nickel phthalocyanine (NiPc) units were preciously controlled. With a molar ratio of 1/1 for the H2Pc and NiPc units in COFs, the catalyst achieved the highest selectivity with a carbon monoxide Faradaic efficiency (FECO) of 95.37% and activity with a turnover frequency (TOF) of 4713.53 h-1. In the multiple H2Pc/NiPc-COFs, the electron-donating features of the H2Pc units provide electron transport to the NiPc centers and thus improved the binding ability of CO2 and intermediates on the NiPc units. The theoretical calculation further confirmed that the H2Pc units donated their electrons to the NiPc units in the frameworks, enhanced the electron density of the Ni sites, and improved the binding ability with Lewis acidic CO2 molecules, thereby boosting the CO2RR performance. This study provides us with new insight into the design of highly active catalysts in electrocatalytic systems.

Preparation of a novel BiVO4-Ni(Ⅱ)/g-C3N4 bifunctional photo electrocatalyst for oxidative and absorptive desulfurization of model fuel

This investigation aims to remove sulfur-based compounds (SBCs) by a combination of absorptive and oxidative desulfurization processes. Accordingly, a series of novel Bi-based bifunctional photo electrocatalysts is prepared by thermal method and used to remove dibenzothiophene (DBT) as a source of SBC from n-heptane as model fuel. The catalysts are used in photo electrocatalytic, photocatalytic, and electrocatalytic desulfurization systems and their effect on oxidative and absorptive processes is compared. The catalysts showed higher efficiency in absorptive desulfurization (ADS) by electrocatalytic desulfurization (EDS) and better results in oxidative desulfurization (ODS) by photocatalytic desulfurization (PDS). Among the results, photoelectrocatalytic desulfurization (POEDS) performed best in DBT removal (94%). The catalyst characterization was carried out with various analyses such as XPS, Raman, FTIR, DRS, TGA, FESEM, TEM, and chronoamperometry. The effect of adding radical scavengers on desulfurization was studied to determine the reaction mechanism. The stability of the selected catalyst is examined by repeating the reaction under optimum reaction conditions.

Earth-Abundant Electrocatalysts for the Oxygen Evolution Reaction Supported on Layered Zirconium Phosphate Nanomaterials

Recently, we have demonstrated improved electrocatalytic activity of layered zirconium phosphate (ZrP) nanomaterials loaded with earth-abundant metal ions suitable as catalysts for the oxygen evolution reaction (OER). We compared the catalytic efficiency of ZrP nanoparticles ion-exchanged with transition metals (Fe, Ni, Co) in the interior of the layers as well as in the external surface to a system in which the metal catalysts are confined exclusively on the external ZrP surface. Linear sweep voltammetry revealed that the electrocatalytic systems with metal catalysts on the external ZrP nanomaterials’ surface had improved OER activity compared to systems with metals intercalated in the ZrP interlayers. This result prompted us to study a system of exfoliated ZrP particles which provide only external surfaces to the electrocatalytic metal ions. A comparison between adsorbed Co or Ni catalysts on ZrP nanoparticles and those same catalysts on exfoliated ZrP nanoplatelets proved that the later systems were more active, with diminished overpotentials and reduced Tafel plot slopes. Comparison between Co and Ni catalyst on ZrP particles with different morphologies (hexagonal platelets, rods, cubes, and spheres) revealed that the more active Co catalysts are those on hexagonal ZrP platelets, whereas the best Ni catalysts are those on ZrP spheres. More recently, efficient OER catalysts were obtained with cobalt porphyrin molecular electrocatalysts both intercalated in ZrP and adsorbed on exfoliated ZrP nanoplatelets. Mixed metal NiFe-intercalated ZrP electrocatalysts at 90% Fe metal content proved to have superior OER electrocatalytic performance (decreased overpotentials, increased mass activities, reduced Tafel slopes) compared to adsorbed counterparts. We are exploring OER activities of other mixed-metal catalysts on ZrP, bifunctional catalysts, and operando synchrotron X-ray absorption spectroscopy studies to elucidate the nature of the active species.

(Invited) Enhanced Photocatalysis on TiO2-Passivated III-V Compound Semiconductors and 2D Material Heterostructures for Water Splitting and CO2 Reduction

We report enhanced photocatalysis for H2 evolution and CO2 reduction using TiO2-passivated InP and GaAs photocathodes.1-4 The TiO2 layer makes the InP semiconductor photochemically stable. This represents a major step forward in photocatalysis, which has typically been limited to metal oxide materials. In addition to making these surfaces stable, the TiO2 film, deposited by atomic layer deposition (ALD), also provides a substantial enhancement in the efficiency of H2 evolution. We find that passivating GaAs with just a few nm of TiO2 produces a shift in the onset potential of H2 evolution by +0.35 V at 1 mA/cm2 and enhances the photocurrent by 32-fold over bare GaAs (at 0 V vs. RHE). Here, thinner TiO2 films produce a larger enhancement than thicker films, which correlates with the higher density of O-vacancies (i.e., Ti3+ surface states) observed in these thinner films using X-ray photoemission spectroscopy (XPS). While TiO2 films 1-5nm thick produce large enhancements, no enhancement is observed for TiO2 thicknesses above 10 nm, which are crystalline and, therefore, considerably more insulating than thinner amorphous TiO2 films.Using transient reflectance spectroscopy (TRS), we measure the photoexcited carrier dynamics in a GaP/TiO2 photoelectrode, as well as the electrostatic field dynamics at this semiconductor-liquid interfaces in situ under various electrochemical potentials.5 Here, the electrostatic fields at the surface of the semiconductor are measured via Franz−Keldysh oscillations (FKO). These spectra reveal that the nanoscale TiO2 protection layer enhances the built-in field and charge separation performance of GaP photoelectrodes.We also demonstrated plasmon-resonant enhancement of photocatalysis on monolayer WSe2.6 In addition, we measured the stacking dependence and resonant interlayer excitation of monolayer WSe2/MoSe2 heterostructures for photocatalytic energy conversion.7 Qiu, J., G. Zeng, M. Ge, S. Arab, M. Mecklenburg, B. Hou, C. Shen, A.V. Benderskii and S.B. Cronin, Correlation of Ti3+ states with photocatalytic enhancement in TiO2-passivated p-GaAs. Journal of Catalysis, 337, 133 (2016).Qiu, J., G.T. Zeng, M.A. Ha, M.Y. Ge, Y.J. Lin, M. Hettick, B.Y. Hou, A.N. Alexandrova, A. Javey and S.B. Cronin, Artificial Photosynthesis on TiO2-Passivated InP Nanopillars. Nano Letters, 15, 6177-6181 (2015).Qiu, J., G.T. Zeng, M.A. Ha, B.Y. Hou, M. Mecklenburg, H.T. Shi, A.N. Alexandrova and S.B. Cronin, Microscopic Study of Atomic Layer Deposition of TiO2 on GaAs and Its Photocatalytic Application. Chemistry of Materials, 27, 7977-7981 (2015).Wang, Y. and S.B. Cronin, Performance Enhancement of TiO2-encapsulated Photoelectrodes Based on III–V Compound Semiconductors, in Ultrathin Oxide Layers for Solar and Electrocatalytic Systems. 2022, Royal Society of Chemistry. p. 103-134.Xu, Z.H., B.Y. Hou, F.Y. Zhao, Z. Cai, H.T. Shi, Y.W. Liu, C.L. Hill, D.G. Musaev, M. Mecklenburg, S.B. Cronin and T.Q. Lian, Nanoscale TiO2 Protection Layer Enhances the Built-In Field and Charge Separation Performance of GaP Photoelectrodes. Nano Letters, 21, 8017-8024 (2021).Chen, J., C.S. Bailey, Y. Hong, L. Wang, Z. Cai, L. Shen, B. Hou, Y. Wang, H. Shi, J. Sambur, W. Ren, E. Pop, and S.B. Cronin., Plasmon-Resonant Enhancement of Photocatalysis on Monolayer WSe2. ACS Photonics, 6, 787 (2019).Chen, J., C.S. Bailey, D. Cui, Y. Wang, B. Wang, H. Shi, Z. Cai, E. Pop, C. Zhou and S.B. Cronin, Stacking Independence and Resonant Interlayer Excitation of Monolayer WSe2/MoSe2 Heterostructures for Photocatalytic Energy Conversion. ACS Applied Nano Materials, DOI:10.1021/acsanm.9b01898 (2020).