The Role of Strontium in CeNiO3 Nano-Crystalline Perovskites for Greenhouse Gas Mitigation to Produce Syngas

The transition metal-based catalysts for the elimination of greenhouse gases via methane reforming using carbon dioxide are directly or indirectly associated with their distinguishing characteristics such as well-dispersed metal nanoparticles, a higher number of reducible species, suitable metal–support interaction, and high specific surface area. This work presents the insight into catalytic performance as well as catalyst stability of CexSr1−xNiO3 (x = 0.6–1) nanocrystalline perovskites for the production of hydrogen via methane reforming using carbon dioxide. Strontium incorporation enhances specific surface area, the number of reducible species, and nickel dispersion. The catalytic performance results show that CeNiO3 demonstrated higher initial CH4 (54.3%) and CO2 (64.8%) conversions, which dropped down to 13.1 and 19.2% (CH4 conversions) and 26.3 and 32.5% (CO2 conversions) for Ce0.8Sr0.2NiO3 and Ce0.6Sr0.4NiO3, respectively. This drop in catalytic conversions post strontium addition is concomitant with strontium carbonate covering nickel active sites. Moreover, from the durability results, it is obvious that CeNiO3 exhibited deactivation, whereas no deactivation was observed for Ce0.8Sr0.2NiO3 and Ce0.6Sr0.4NiO3. Carbon deposition during the reaction is mainly responsible for catalyst deactivation, and this is further established by characterizing spent catalysts.

Application of Pier Waste Sludge for Catalytic Activation of Proxy-monosulfate and Phenol Elimination From a Petrochemical Wastewater

This investigation aimed to remove phenol from a real wastewater (taken from a petrochemical company) by activating peroxy-monosulfate (PMS) using catalysts extracted from pier waste sludge. The physical and chemical properties of the catalyst were evaluated by FE-SEM/EDS, XRD, FTIR, and TGA/DTG tests. The functional groups of O-H, C-H, CO32-, C-H, C-O, N-H, and C-N were identified on the catalyst surface. Also, the crystallinity of the catalyst before and after reaction with petrochemical wastewater was 103.4 nm and 55.8 nm, respectively. Operational parameters of pH (3-9), catalyst dose (0-100 mg/L), phenol concentration (50-250 mg/L), and PMS concentration (0-250 mg/L) were tested to remove phenol. The highest phenol removal rate (94%) was obtained at pH=3, catalyst dose of 80 mg/L, phenol concentration of 50 mg/L, PMS concentration of 150 mg/L, and contact time of 150 min. Phenol decomposition in petrochemical wastewater followed the first-order kinetics (k> 0.008 min-1, R2> 0.94). Based on the reported results, it was found that the pH factor is more important than other factors in phenol removal. The catalyst stability test was performed for up to five cycles and phenol removal in the fifth cycle was reduced to 42%. Also, the energy consumption in this study was 77.69 kw.h/m3. According to the results, the pier waste sludge catalyst/PMS system is a critical process for eliminating phenol from petrochemical wastewater.

The Influence of Transitional Metal Dopants on Reducing Chlorine Evolution during the Electrolysis of Raw Seawater

Electrocatalytic water splitting is a possible route to the expanded generation of green hydrogen; however, a long-term challenge is the requirement of fresh water as an electrolyzer feed. The use of seawater as a direct feed for electrolytic hydrogen production would alleviate fresh water needs and potentially open an avenue for locally generated hydrogen from marine hydrokinetic or off-shore power sources. One environmental limitation to seawater electrolysis is the generation of chlorine as a competitive anodic reaction. This work evaluates transition metal (W, Co, Fe, Sn, and Ru) doping of Mn-Mo-based catalysts as a strategy to suppress chlorine evolution while sustaining catalytic efficiency. Electrochemical evaluations in neutral chloride solution and raw seawater showed the promise of a novel Mn-Mo-Ru electrode system for oxygen evolution efficiency and enhanced catalytic activity. Subsequent stability testing in a flowing raw seawater flume highlighted the need for improved catalyst stability for long-term applications of Mn-Mo-Ru catalysts. This work highlights that elements known to be selective toward chlorine evolution in simple oxide form (e.g., RuO2) may display different trends in selectivity when used as isolated dopants, where Ru suppressed chlorine evolution in Mn-based catalysts.

Recent Advances in the Mitigation of the Catalyst Deactivation of CO2 Hydrogenation to Light Olefins

The catalytic conversion of CO2 to value-added chemicals and fuels has been long regarded as a promising approach to the mitigation of CO2 emissions if green hydrogen is used. Light olefins, particularly ethylene and propylene, as building blocks for polymers and plastics, are currently produced primarily from CO2-generating fossil resources. The identification of highly efficient catalysts with selective pathways for light olefin production from CO2 is a high-reward goal, but it has serious technical challenges, such as low selectivity and catalyst deactivation. In this review, we first provide a brief summary of the two dominant reaction pathways (CO2-Fischer-Tropsch and MeOH-mediated pathways), mechanistic insights, and catalytic materials for CO2 hydrogenation to light olefins. Then, we list the main deactivation mechanisms caused by carbon deposition, water formation, phase transformation and metal sintering/agglomeration. Finally, we detail the recent progress on catalyst development for enhanced olefin yields and catalyst stability by the following catalyst functionalities: (1) the promoter effect, (2) the support effect, (3) the bifunctional composite catalyst effect, and (4) the structure effect. The main focus of this review is to provide a useful resource for researchers to correlate catalyst deactivation and the recent research effort on catalyst development for enhanced olefin yields and catalyst stability.

Activation Mechanism of Nickel(0) N-Heterocyclic Carbene Catalysts Stabilized by Fumarate Ligands

Nickel(0) catalysts of N-heterocyclic carbenes (NHCs) that are stabilized by electronic deficient alkenes possess desirable properties of air tolerance and ease of handling while also retaining high catalytic activities. Since catalyst stability often comes at the expense of catalytic activity, we have undertaken a detailed study of the activation mechanism of a new IMes-nickel(0) catalyst stabilized by di-(o-tolyl) fumarate that converts the stable pre-catalyst form into a catalytically active species. Computational evaluation provided evidence against a simple ligand exchange as the activation mechanism, and a stoichiometric activation process that covalently modifies the stabilizing ligand was identified. A detailed computational picture for the activation process was developed, with predictive insights that explain the catalyst features that lead to both active and inactive precatalysts.

Switchable Structure Promoted Leaching Free Atomically Dispersed Pt Catalyst for Low Carbon Biomass Polyol Oxidation

Achieving efficient catalytic conversion over heterogeneous catalyst with excellent resistance against leaching is still a grand challenge for sustainable chemical synthesis in aqueous solution. Herein, we devised a leaching free atomically dispersed Pt1/hydroxyapatite (HAP) catalyst with unique switchable structure via a simple and green in-situ anchoring strategy. Gratifyingly, this robust Pt1/HAP catalyst exhibits remarkable catalytic selectivity and catalyst stability for the selective oxidation of C2-C4 bio-polyols (e.g., ethylene glycol, propanediol, glycerol and butanediol) to corresponding primary hydroxy acids. X-ray absorption spectroscopy, in-situ Fourier Transform infrared spectroscopy, density functional theory calculation and kinetics study elucidated that the switchable Pt-(O-P) linkages with strong electronic-withdrawing function of PO43− (Pt1-OPO43− active site) not only realize the activation of C-H bond, but also destabilize the transition state from adsorbed hydroxy acids toward the C-C cleavage, resulting in the sharply increased selectivity of hydroxy acids. Moreover, the strong PO43−-coordination effect, originating from the enhanced interaction between positively charged Pt1 and negatively charged OPO43−, provides electrostatic stabilization for the atomically dispersed Pt, ensuring the highly efficient catalysis of Pt1/HAP for over 160 hours without metal leaching. This finding opens up new opportunities for efficient upgrading of bio-polyols over atomically dispersed catalysts.