Construction of Dual-Active Sites by Interfacing with Polyhydroxy Fullerene on Nickel Hydroxide Surfaces to Promote CO2 Deep Photoreduction to CH4.

Due to the complex series of elementary steps involved, achieving deep photoreduction of CO2 to multielectron products such as CH4 remains a challenging task. Therefore, it is crucial to strategically design catalysts that facilitate the controlled formation of the crucial intermediates and provide precise control over the reaction pathway. Herein, we present a pioneering approach by employing polyhydroxy fullerene (PHF) molecules to modify the surface of Ni(OH)2, creating stable and effective synergistic sites to enhance the formation of CH4 from CO2 under light irradiation. As a result, the optimized PHF-modified Ni(OH)2 cocatalyst achieves a CH4 production rate of 455 µmol g-1 h-1, with an electron-based selectivity of approximately 60%. The combination of in situ characterizations and theoretical calculations reveals that the hydroxyl species on the surface of PHF can participate in stabilizing crucial intermediates and facilitating water activation, thereby altering the reaction pathway to form CH4 instead of CO. This study provides a novel approach to regulating the selectivity of photocatalytic CO2 reduction by exploring molecular surface modification through interfacing with functionalized carbon clusters.

A Chiral Metal-Organic Framework Prepared on Large-Scale for Sensitive and Enantioselective Fluorescence Recognition.

MOF-based luminescent sensors have garnered considerable attention due to their potential in recognition and discrimination with high sensitivity, selectivity, and fast response in the last decades. Herein, this work describes the bulk preparation of a novel luminescent homochiral MOF, namely, [Cd(s-L)](NO3)2 (MOF-1), from an enantiopure pyridyl-functionalized ligand with rigid binaphthol skeleton under mild synthetic condition. Except for the features of porosity and crystallinity, the MOF-1 has also been characterized with water-stability, luminescence, and homochirality. Most important, the MOF-1 exhibits highly sensitive molecular recognition toward the4-nitrobenzoic acid (NBC) and moderate enantioselective detection of proline, arginine, and 1-phenylethanol.

Chloramphenicol-activated electro-chemiluminescent behavior of BNQDs-Ru(phen)32+ system for ultra-sensitive sensing of chloramphenicol in pharmaceutical and milk samples.

To improve the sensitivity for electro-chemiluminescent (ECL) detection of chloramphenicol (CAP), a common broad-spectrum antibiotic, boron nitride quantum dots (BNQDs) were prepared with excellent photoelectric property and low toxicity. After its structure and electrochemical property were investigated in detail, it was noted that the ECL signal of Ru(Phen)32+could be strengthened by the proposed BNQDs, which was further activated by ten's times in the presence of CAP. Under the optimized conditions, there was an excellent linear relationship between ΔECL and lgcCAPin a wide linear range from 1.0 × 10-10to 1.0 × 10-6mol l-1CAP. The detection limit was super-low to be 3.3 × 10-11mol l-1(S/N = 3). When applied for CAP detection in real pharmaceutical and food samples, the recoveries were between 97.8% and 105.7% with R.S.D. less than 3.3%. A possible CAP-activated ECL mechanism of BNQDs-Ru(phen)32+was also proposed. This work will offer a great potential for efficient monitoring of CAP pollution and clinical diagnosing of CAP-related diseases in future.

Chloramphenicol-activated electro-chemiluminescent behavior of BNQDs-Ru(phen)32+ system for ultra-sensitive sensing of chloramphenicol in pharmaceutical and milk samples.

To improve the sensitivity for electro-chemiluminescent (ECL) detection of chloramphenicol (CAP), a common broad-spectrum antibiotic, boron nitride quantum dots (BNQDs) were prepared with excellent photoelectric property and low toxicity. After its structure and electrochemical property were investigated in detail, it was noted that the ECL signal of Ru(Phen)32+ could be strengthened by the proposed BNQDs, which was further activated by ten's times in the presence of CAP. Under the optimized conditions, there was an excellent linear relationship between △ECL and lgcCAP in a wide linear range from 1.0×10-10 to 1.0×10-6 mol/L CAP. The detection limit was super-low to be 3.3×10-11 mol/L (S/N=3). When applied for CAP detection in real pharmaceutical and food samples, the recoveries were between 97.8 and 105.7 % with R.S.D. less than 3.3%. A possible CAP-activated ECL mechanism of BNQDs-Ru(phen)32+ was also proposed. This work will offer a great potential for efficient monitoring of CAP pollution and clinical diagnosing of CAP-related diseases in future.

One-dimensional nitrogen doped porous carbon nano-array arranged by carbon nanotubes for electrochemical sensing ascorbic acid, dopamine and uric acid simultaneously.

In this work, one-dimensional nitrogen doped porous carbon nano-arrays arranged by carbon nanotube (1D CNTs@NPC) were first constructed, using a coating technology at room temperature and followed by high temperature carbonization. It was expected that the resulting glassy carbon electrodes modified by 1D CNTs@NPC (CNTs@NPC/GCE) could express different electrochemical responses to ascorbic acid (AA), dopamine (DA), uric acid (UA), by virtue of the synergistic-improved effect between CNTs and NPC. Under the optimized conditions, there were excellent analytical parameters for CNTs@NPC/GCE to detect AA, DA and UA, i.e. a wide linear range of 40-2100µM for AA, 0.5-49µM for DA and 3-50µM for AA with low detection limits of 0.36µM, 0.02µmol l-1and 0.57µM respectively. Importantly, the proposed CNTs@NPC/GCE was efficiently applied to determine AA, DA and UA in some real samples with high stability, reproducibility and selectivity. This work will offer an efficient potential for diagnosing ascorbic acid, dopamine or uric acid-related diseases on clinical testing in future.

Electrocatalytic oxygen evolution with a cobalt complex.

The development of an earth-abundant, first-row water oxidation catalyst that operates at a high TOF and a low overpotential remains a fundamental chemical challenge. Cobalt complexes are important members of water oxidation catalysts. Herein, we report a cobalt-based robust homogeneous water oxidation catalyst, which can electrocatalyze water oxidation at a high pH and a low overpotential (η = 520 mV) in phosphate buffer. This homogeneous system exhibits a high turnover frequency (about 5 s-1) of catalyzing water oxidation to produce oxygen at η = 720 mV. We speculate the mechanism of the reaction that O-O bond formation prefers a HO-OH coupling in catalytic water oxidation.

Heterometallic aggregates of copper(I) with metalloligand Sn(edt)2 (edt = ethane-1,2-dithiolate): syntheses and structures of [Sn(edt)2Cl(mu-I)(mu3-I)(CuPPh3)3], [Sn(edt)2(mu-Br)2(mu3-Br)2(CuPPh3)4], and [{Sn(edt)2}3(mu-OH)3Cu5(PPh3)8][PF6]2.

The treatment of a slurry of an equimolar mixture of [Sn(edt)(2)] (edt = ethane-1,2- dithiolate) and [Et(4)N]Cl.xH(2)O with CuI in the presence of PPh(3) gave a tetranuclear compound, [Sn(edt)(2)Cl(mu-I)(mu(3)-I)(CuPPh(3))(3)] (1), which consists of a rectangular-pyramidal [Sn(edt)(2)Cl](-) moiety ligated by three [Cu(PPh(3))](+) fragments via the sulfur atoms of the edt(2-) ligands. The treatment of a slurry of [Sn(edt)(2)] and excess [Et(4)N]Br with [Cu(MeCN)(4)][PF(6)] in the presence of PPh(3) afforded a pentanuclear compound, [Sn(edt)(2)(mu-Br)(2)(mu(3)-Br)(2)(CuPPh(3))(4)] (2), which comprises two [(CuPPh(3))(2)(mu-Br)](+) fragments symmetrically ligating an octahedral trans-[Sn(edt)(2)Br(2)](2-) moiety via the sulfur and bromide atoms. Reaction of [Sn(edt)(2)] with [Cu(MeCN)(4)][PF(6)] and PPh(3) in a mixed MeCN/CH(2)Cl(2) solution yielded a novel octanuclear compound, [{Sn(edt)(2)}(3)(mu-OH)(3)Cu(5)(PPh(3))(8)][PF(6)](2) (3), which may be described as a triangular [{Sn(edt)(2)}(3)(mu-OH)(3)](3-) core chelated by three [Cu(PPh(3))(2)](+) species and capped by two [Cu(PPh(3))](+) species. The luminescent properties of compounds 1, 2, and 3 were investigated in a CH(2)Cl(2) solution at room temperature. Upon excitation at lambda > 360 nm, these compounds are luminescent in CH(2)Cl(2) solution with emissions having maxima at 422, 515, and 494 nm, respectively.

Tetra-ethyl-ammonium trichlorido(η-p-cymene)ruthenate(II).

In the title salt, [(C(2)H(5))(4)N][RuCl(3)(C(10)H(14))], the Ru(II) atom shows an octa-hedral coordination in which the aromatic ring of the p-cymene mol-ecule occupies three coordination positions.

Bis(η-ethyl-ene)[aza-nidediylbis(diiso-propyl-phosphine selenide)-κSe,Se']iridium(III).

In the title compound, [Ir(η(2)-C(2)H(4))(2)(C(12)H(28)NP(2)Se(2))], the central Ir atom is chelated by the [N((i)Pr(2)PSe)(2)](-) ligand via two Se atoms and is coordinated by two η(2)-ethyl-ene mol-ecules via four C atoms in an octa-hedral coordination geometry.

Selective response of dopamine in the presence of ascorbic acid at multi-walled carbon nanotube modified gold electrode.

The acid-treated multi-walled carbon nanotubes (MWNTs), which were modified on the surface of gold electrode, offers substantial improvements in voltammetric sensitivity and selectivity towards the determination of dopamine (DA). It can inhibit the voltammetric response of ascorbic acid (AA) while the redox reaction of dopamine is promoted. When a differential pulse voltammetric (DPV) technique was used, the peak separation between DAs and AAs was 244 mV. Based on this, a selective method could be constructed to detect DA in the presence of 1,000 times higher concentration of AA. The effect of various experimental parameters on the voltammetric response of dopamine was investigated. Under the chosen conditions, the peak currents are correspondent linearly to the concentrations of DA in the range of 5 x 10(-7) approximately 4 x 10(-4) mol L(-1) with a limit of detection of 2 x 10(-7) mol L(-1). The proposed method can be applied to detect DA in real samples.