Nitrate Reduction by NiFe-LDH/CeO2: Understanding the Synergistic Effect between Dual-Metal Sites and Dual Adsorption.

Electrocatalytic nitrate reduction reaction (EC-NITRR) shows a significant advantage for green reuse of the nitrate (NO3-) pollutant. However, the slow diffusion reaction limits the reaction rate in practical EC-NITRR, causing an unsatisfactory ammonia (NH3) yield. In this work, a multifunctional NiFe-LDH/CeO2 with the dual adsorption effect (physisorption and chemisorption) and dual-metal sites (Ce3+ and Fe2+) was fabricated by the electrodeposition method. NiFe-LDH/CeO2 performed an expected ability of enrichment for NO3- through the pseudo-first-order and pseudo-second-order kinetic models, and the polymetallic structure provided abundant sites for effective reaction of NO3-. At-0.6 V vs RHE, the ammonia (NH3) yield of NiFe-LDH/CeO2 reached 335.3 µg h-1 cm-2 and the selectivity of NH3 was 24.2 times that of NO2-. The nitrogen source of NH3 was confirmed by 15NO3- isotopic labeling. Therefore, this work achieved the recycling of the NO3- pollutant by synergy of enrichment and catalysis, providing an alternative approach for the recovery of NO3- from wastewater.

Strengthening the Stability of the Reconstructed NiOOH Phase for 5-Hydroxymethylfurfural Oxidation.

Electrochemical oxidation of biomass-derived 5-hydroxymethylfurfural (HMF) is a promising approach to produce high-value chemicals such as 2,5-furandicarboxylic acid (FDCA). However, the undesirable stability of catalysts commonly limits its potential application value. In this work, NiOOH derived from Ni(OH)2 was determined as the main catalytic site for HMF oxidation, but the collapse of Ni(OH)2 caused severe instability during the electrocatalytic process because of the crystal structure mismatch between NiOOH and Ni(OH)2. The implantation of Ce in Ni(OH)2 (Ce-Ni(OH)2) was successfully realized to address the stability issue of bare Ni(OH)2, since the larger ion radius of Ce could increase the Ni-O bond length and d-spacing. As a result, the activity of 14%Ce-Ni(OH)2 has not obviously decayed after the 50 cyclic voltammetry (CV)-cycle test. HMF conversion is close to 100%, and the Faraday efficiency (FE) reaches 86.6% at the potential of 0.45 V vs Ag/AgCl. This study provides a new strategy to design stable catalysts for the conversion of biomass derivatives.

CeO2/Ni-MOF with Synergistic Function of Enrichment and Activation: Efficient Reduction of 4-Nitrophenol Pollutant to 4-Aminophenol.

The conversion of organic pollutants to value-added chemicals has been considered as a sustainable approach to solve environmental problems. However, it is still a challenge to construct a suitable heterogeneous catalyst that can synchronously achieve the enrichment and activation of organic pollutants (such as 4-nitrophenol, 4-NP). Here, an organic-inorganic hybrid catalyst (CeO2/Ni-MOF) was successfully fabricated for efficiently reducing 4-NP to 4-aminophenol (4-AP) with water as the hydrogen source. Based on the synergistic effect of Ni-MOF (adsorption action) and CeO2 (active sites), CeO2/Ni-MOF could achieve a reaction rate of 1.102 µmol min-1 mg-1 with an ultrahigh Faraday efficiency (FE) (99.9%) and conversion (97.6%). In addition, the catalytic mechanism of 4-NP reduction over CeO2/Ni-MOF was elaborated in depth. This work presents a new avenue for the effective reduction of pollutants and provides a new strategy for designing high-performance catalysts for rare-earth metals.

In Situ Electrochemical Reconstitution of CF-CuO/CeO2 for Efficient Active Species Generation.

Achievement of the intrinsic activity by in situ electrochemical reconstruction has been becoming a great challenge for designing a catalyst. Herein, an effective electrochemical strategy is proposed to reconstruct the surface of the CF-CuO/CeO2 precursor. Under the stimulation of oxidative/reductive potential, abundant active sites were successfully generated on the surface of CF-CuO/CeO2. Remarkably, the implantation of oxygen vacancy-rich CeO2 synergistically optimizes the chemical composition and electronic structure of CF-CuO/CeO2, greatly promoting the generation of active species. Systematic electrochemical experiments indicate that the superior catalytic performance of reconstructed CF-CuO/CeO2 could be attributed to CuOOH/CeO2 and Cu2O/Ce2O3 active species, respectively. The oxidative-/reductive-activated CF-CuO/CeO2 was further employed in a paired cell for the synergistic catalysis of hydroxymethylfurfural oxidation with 4-nitrophenol hydrogenation. As a result, nearly 100% Faraday efficiency for furandicarboxylic acid/4-aminophenol production was achieved in the paired system (-0.9 V vs Ag/AgCl, 1.5 h). Therefore, the electrochemical reconstruction via oxidative/reductive activation has been confirmed as a feasible approach to significantly excite the intrinsic activity of a catalyst.

Controllable evolution of NiOOH/Au3+ active species for the oxidation of 5-hydroxymethylfurfural.

To induce the generation of active species at the metal-carrier interface, a new synthetic strategy was successfully developed to reconstruct the Ni MOF-Au via electrochemical activation. This unique configuration not only obtained high-valence NiOOH-Au3+ species, but also stably anchored the Au nanoparticles on the surface of the catalyst. As a result, nearly 99.8% FDCA yield and 100% Faraday efficiency of FDCA were achieved at the optimal potential of 1.57 V vs. RHE. Therefore, this electrochemical reconstruction provides new insights for the development of efficient catalysts in other heterogeneous catalytic reactions.

Electrocatalytic reduction of 4-nitrophenol over Ni-MOF/NF: understanding the self-enrichment effect of H-bonds.

The chemical adsorption and active sites play a key role in electrocatalysis, so Ni-MOF/nickel foam was fabricated for efficiently reducing 4-nitrophenol (4-NP) without any sacrificial agents. The coordinated water molecules induced the formation of hydrogen bonds (H-bonds) with the nitro group, contributing to the self-enrichment of 4-NP. The reaction rate reached 0.351 µmol min-1 mg-1. Therefore, this work provides a new insight into the H-bond effect in the field of electrocatalysis.

Ag/Ni-MOF heterostructure with synergistic enrichment and activation properties for electrocatalytic reduction of 4-nitrophenol.

The synchronous optimization of adsorption and activity dominates the practical performance in electrocatalysis, so Ag/Ni-MOF/Ni foam was synthesized for expediting 4-nitrophenol (4-NP) reduction under mild and green conditions. The synergistic combination of selective adsorption (Ni-MOF) and sites (Ag) contributed to the excellent performance of 4-NP reduction. The 4-NP (25 mM) conversion and Faraday efficiency have been achieved up to 98.4% and 99.8%, respectively. Therefore, this work provides a feasible approach for synergistic enrichment and activation to convert pollutants.

Biothiol-Functionalized Cuprous Oxide Sensor for Dual-Mode Sensitive Hg2+ Detection.

Hg2+ ions are one of the highly poisonous heavy metal ions in the environment, so it is urgent to develop rapid and sensitive detection platforms for detecting Hg2+ ions. In this work, a novel electrochemical and photoelectrochemical dual-mode sensor (l-Cys-Cu2O) was successfully fabricated, and the sensor exhibits a satisfactory detection limit (0.2 and 0.01 nM) for the detection of Hg2+, which is far below the dangerous limit of the U.S. Environmental Protection Agency. The linear ranges of dual-mode Hg2+ detections were 0.33-3.3 and 0.17-1.33 µM, respectively. Moreover, the sensor shows desirable stability, selectivity, and reproducibility for detecting Hg2+ ions. For river water samples, the recoveries of 96.6-101.4% (electrochemical data) and 93.0-105.6% (photoelectrochemical data) were obtained, indicating that the sensor could be successfully applied in the determination of Hg2+ ions in environmental water. Therefore, the designed sensor has a potential in the trace-level detection of Hg2+ ions.