CN111171083B - Nickel-sulfur complex containing PCNCP diphosphine ligand and preparation method and application thereof - Google Patents

Nickel-sulfur complex containing PCNCP diphosphine ligand and preparation method and application thereof Download PDF

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CN111171083B
CN111171083B CN202010039439.0A CN202010039439A CN111171083B CN 111171083 B CN111171083 B CN 111171083B CN 202010039439 A CN202010039439 A CN 202010039439A CN 111171083 B CN111171083 B CN 111171083B
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赵培华
李建荣
谷晓丽
荆兴斌
高祎
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North University of China
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Abstract

The invention relates to the field of bio-enzyme bionic chemistry and new energy materials, in particular to a nickel-sulfur complex containing PCNCP diphosphine ligand and a preparation method and application thereof. The nickel-sulfur complex containing PCNCP diphosphine ligand { (Ph) 2 PCH 2 ) 2 NR}Ni(SCH 2 CH 2 S), wherein R is benzyl CH 2 C 6 H 5 Pyridine methyl CH 2 C 5 H 4 And N is added. The invention also provides a preparation method of the nickel-sulfur complex containing the PCNCP diphosphine ligand. The preparation method is simple and quick, has simple operation process, mild reaction conditions, high reaction rate, single product and high yield, and can be suitable for preparing various novel nickel-sulfur complexes containing different PCNCP diphosphine ligands and different disulfide bridge frameworks. The nickel-sulfur complex containing the PCNCP diphosphine ligand prepared by the invention has an effective electrocatalytic hydrogen production function and a good potential application value in the presence of strong acid and weak acid.

Description

Nickel-sulfur complex containing PCNCP diphosphine ligand and preparation method and application thereof
Technical Field
The invention relates to the field of bio-enzyme bionic chemistry and new energy materials, in particular to a nickel-sulfur complex containing PCNCP diphosphine ligand, a preparation method thereof and application thereof in catalytic hydrogen production.
Background
Since fossil fuel is a non-renewable resource, with increasing severe consumption year by year, the world will face the problem of energy shortage. Meanwhile, the combustion of fossil fuels can generate harmful gases such as carbon dioxide and sulfur dioxide, thereby causing serious pollution to the environment. The national planning clearly provides and deeply promotes the energy revolution, accelerates the energy technology innovation, and builds a clean, low-carbon, safe and efficient modern energy system. Hydrogen is considered as the best fuel of the next generation of clean and renewable energy, and the existing hydrogen production technology comprises chemical catalytic cracking, photo/electrochemical catalytic water decomposition and the like, wherein the electrochemical technology has the advantages of high conversion efficiency, environmental protection and the like, so that the hydrogen is widely used. At present, noble metal is the best hydrogen production catalyst for industrial water electrolysis hydrogen production, but the noble metal is expensive and scarce in resources, so that the search for a non-noble metal catalyst with high catalytic activity and the application of the non-noble metal catalyst in the field of photo/electrochemical catalytic hydrogen production are research hotspots in the field of new energy materials at present. In nature, natural iron hydrogenase and nickel iron hydrogenase have the functions of efficiently and quickly catalyzing and reducing protons into hydrogen because of the unique iron-sulfur or nickel-sulfur catalytic metal center.
Based on the above, researchers have conducted significant bio-enzyme bionic chemical research on the basic structure and catalytic function of the catalytic metal center of natural ferro-iron hydrogenase and ferro-nickel hydrogenase, and prepared a large amount of iron-sulfur complexes and a small amount of nickel-sulfur complexes, so as to find a non-noble metal catalyst capable of effectively reducing protons to produce hydrogen. Among these metal sulfides, hydrogenase mimetics in which bidentate ligands coordinate to the same metal atom in a chelating manner have been recognized as one of the most promising non-noble metal catalysts for efficient catalytic proton reduction to hydrogen. However, a nickel-sulfur complex containing PCNCP diphosphine ligand chelating coordination and a dithiol bridge skeleton and application of the nickel-sulfur complex which is expected to be used as a non-noble metal catalyst and can effectively catalyze proton reduction to prepare hydrogen have not been reported so far. In addition, among bidentate ligands, the PCNCP bisphosphine ligand (Ph) 2 CH 2 ) 2 NR is a cheap and easily-obtained organic phosphine ligand with adjustable properties, nitrogen atom contained in the ligand and connected with the nitrogen atomSubstituent species regulate the nature of the ligand itself, and are therefore a very useful class of bidentate ligands in metal coordination chemistry.
Disclosure of Invention
Based on the technical analysis, the invention provides a nickel-sulfur complex containing PCNCP diphosphine ligand and a preparation method thereof aiming at the problems of lower hydrogen production performance, complex structural synthesis and the like of the prior non-noble metal catalysts such as iron-sulfur complex and nickel-sulfur complex, and realizes the potential application value of effectively catalyzing proton reduction hydrogen production. The synthesis method is simple, simple to operate, mild in condition and high in yield, and can be used for preparing various nickel-sulfur complexes containing different PCNCP diphosphine ligands and different dithiol bridge frameworks. The nickel-sulfur complex prepared by the invention has the function of electrocatalytic proton reduction hydrogen production in the presence of strong acid (trifluoroacetic acid) or weak acid (acetic acid).
The invention is realized by the following technical scheme: the PCNCP diphosphine ligand in the complex is coordinated to a mononuclear nickel atom in a chelating manner, and the chemical formula of the simulant is { (Ph) 2 PCH 2 ) 2 NR}Ni(SCH 2 CH 2 S), the molecular structural formula is as follows:
Figure BDA0002367211360000021
wherein R is benzyl CH 2 C 6 H 5 Pyridine methyl CH 2 C 5 H 4 N。
The invention further provides a preparation method of the nickel-sulfur complex containing the PCNCP diphosphine ligand, which comprises the following steps:
1) at room temperature, [ Ph ] is 2 P(CH 2 OH) 2 ] + Cl - And triethylamine are respectively added into a mixed solvent of water and ethanol;
2) adding NH into the reaction system in the step 1) 2 R, heating, refluxing and reacting for 3-4 hours, extracting with dichloromethane, and removing a dichloromethane solvent;
3) extracting the residueSeparating with preparative thin layer chromatography or column chromatography using mixed solvent as developing agent, collecting main color band to obtain PCNCP diphosphine ligand (Ph) 2 PCH 2 ) 2 NR；
4) At room temperature, adding NiCl 2 ·6H 2 Adding O into an ethanol solvent;
5) coupling the PCNCP bisphosphine ligand (Ph) 2 PCH 2 ) 2 Adding NR into a dichloromethane solvent, then dropwise adding into the reaction system in the step 4), stirring and reacting for 5 minutes at room temperature, and removing the dichloromethane solvent;
6) the residue was washed with diethyl ether to give a precursor nickel chloride complex containing PCNCP bisphosphine ligand { (Ph) 2 PCH 2 ) 2 NR}NiCl 2 ；
7) Under room temperature conditions, precursor nickel chloride complex containing PCNCP diphosphine ligand { (Ph) 2 PCH 2 ) 2 NR}NiCl 2 Adding ethanedithiol into a dichloromethane solvent in sequence;
8) adding triethylamine into the reaction system in the step 7), stirring and reacting for 1 hour at room temperature, and removing a dichloromethane solvent;
9) extracting the residue, performing preparative thin layer chromatography with mixed solvent as developing solvent, and collecting main color band to obtain nickel-sulfur complex { (Ph) containing PCNCP diphosphine ligand 2 PCH 2 ) 2 NR}Ni(SCH 2 CH 2 S); wherein R is benzyl CH 2 C 6 H 5 Pyridine methyl CH 2 C 5 H 4 N。
The invention further provides a preparation route of the nickel-sulfur complex containing the PCNCP diphosphine ligand, which comprises the following steps:
Figure BDA0002367211360000022
in specific application, in the preparation method, the PCNCP diphosphine ligand is (Ph) 2 PCH 2 ) 2 NR, R being CH 2 C 6 H 5 Or CH 2 C 5 H 4 N，
As a preferable embodiment of the preparation method of the nickel-sulfur complex containing PCNCP diphosphine ligand, the NH in the steps 1) and 2) is 2 R, triethylamine, [ Ph ] 2 P(CH 2 OH) 2 ] + Cl - And the using amount ratio of the mixed solvent of water and ethanol is 2 mmol/12 mmol/4.4-4.8 mmol/30-45 mL.
As one of the preferable embodiments of the preparation method of the nickel-sulfur complex containing PCNCP diphosphine ligand, the NiCl in the steps 4) and 5) is adopted 2 ·6H 2 O、(Ph 2 PCH 2 ) 2 The dosage ratio of NR, ethanol and dichloromethane is 0.7mmol: 0.84-0.95 mmol: 10-15 mL: 5-10 mL.
As a preferred embodiment of the process for the preparation of the nickel-sulfur complexes containing PCNCP bisphosphine ligands according to the invention, ethanedithiol, { (Ph) in Steps 7) and 8) 2 PCH 2 ) 2 NR}NiCl 2 The dosage ratio of the triethylamine to the dichloromethane is 0.24 mmol/0.29-0.36 mmol/0.48-0.53 mmol/15-20 mL.
As a preferable example of the preparation method of the nickel-sulfur complex containing PCNCP diphosphine ligand, the residue extracting agents in the steps 3) and 9) are dichloromethane; the preparative thin-layer chromatography is silica gel G thin-layer chromatography separation, and the column chromatography is 100-200 mesh neutral alumina column chromatography separation; the developing solvent is a mixed solvent of petroleum ether and ethyl acetate in a volume ratio of 20:1, or a mixed solvent of dichloromethane and ethyl acetate in a volume ratio of 1:1 and 15: 1.
As a preferable example of the specific embodiment of the preparation method of the nickel-sulfur complex containing PCNCP diphosphine ligand, the reflux temperature in the step 2) is 76-80 ℃.
As a preferable mode in the specific embodiment of the preparation method of the nickel-sulfur complex containing PCNCP diphosphine ligand, the solvent removal in the steps 2), 5) and 8) adopts a reduced pressure rotary evaporation mode.
The invention further provides application of the nickel-sulfur complex containing the PCNCP diphosphine ligand in electrochemical catalysis of reduction of protonic acid into hydrogen.
The invention also provides application of the nickel-sulfur complex prepared by the preparation method of the nickel-sulfur complex containing PCNCP diphosphine ligand in electrocatalysis of protonic acid reduction to hydrogen.
The catalytic performance test of the nickel-sulfur complex containing the PCNCP diphosphine ligand adopts a classical electrochemical cyclic voltammetry method: the test was carried out on a CHI 660E electrochemical instrument using a glassy carbon electrode of 3mm diameter as the working electrode, a platinum wire as the counter electrode, and non-aqueous Ag/AgNO 3 (0.01M AgNO 3 /0.1M n-Bu 4 NPF 6 /CH 3 CN) is a classical three-electrode system of a reference electrode, and the measurement is carried out in a cylindrical groove and under the nitrogen atmosphere; before each test, 0.05 mu m of aluminum oxide powder is used for polishing a glassy carbon electrode, then ultrasonic cleaning is carried out in water, finally acetone washing and cold air blow-drying are carried out; the solvent of the test system is chromatographic pure acetonitrile, the sample concentration is 1mmol/L, and the supporting electrolyte is n-Bu with the concentration of 0.1mol/L 4 NPF 6 The protonic acid is trifluoroacetic acid or acetic acid with a sweep rate of 100mV s of 0, 2, 4, 6, 8 and 10mmol/L -1 The potentials obtained by the test are all ferrocene-corrected reduction potentials. Meanwhile, according to a calculation formula k of catalytic efficiency TOF of hydrogen evolution reaction obs (TOF)＝1.94ν(i cat /i p ) 2 The theoretical catalytic efficiency TOF value can be obtained, wherein i p The reduction current without addition of protonic acid, i cat Is the magnitude of the catalytic current generated when a certain concentration of protonic acid is added.
The catalytic performance is represented as: in an electrochemical test system containing 1mmol/L of nickel-sulfur complex, with the continuous increase of the concentration of protonic acid, the peak current of a reduction peak is continuously increased, the corresponding peak potential is not changed greatly, and the phenomenon is the obvious characteristic of homogeneous catalytic hydrogen evolution. At the same time, the theoretical catalytic efficiency TOF of the nickel-sulfur complexes increases linearly with increasing concentration of the protic acid.
Compared with the prior art, the nickel-sulfur complex containing PCNCP diphosphine ligand has the following beneficial effects:
(1) the nickel-sulfur complex prepared by the invention is a new compound, and compared with the existing commonly used diphosphine ligand, the PCNCP diphosphine ligand contained in the structure is a diphosphine ligand which is easy to prepare and adjustable in property, and the nitrogen atom contained in the ligand and the substituent group connected with the nitrogen atom can adjust the electron and space effect, the proton capturing and transferring capability of the prepared complex, so that the catalytic hydrogen production performance of the prepared complex can be adjusted more purposefully in function.
(2) The preparation method provided by the invention is simple and convenient to operate, mild in condition, fast in reaction, single in product and high in yield, and can be suitable for preparing various novel nickel-sulfur complexes containing different PCNCP diphosphine ligands and different disulfide bridge frameworks.
(3) Compared with the similar complex disclosed in the prior art, the nickel-sulfur complex prepared by the invention has the function of electrochemically catalyzing proton reduction to hydrogen under the conditions of strong acid (such as trifluoroacetic acid) and weak acid (such as acetic acid), and has potential industrial application value.
Drawings
FIG. 1 is a nuclear magnetic resonance hydrogen spectrum of a nickel-sulfur complex 1 in example 1 of the present invention.
FIG. 2 is a NMR phosphorus spectrum of nickel-sulfur complex 1 in example 1 of the present invention.
FIG. 3 is a graph of electrochemical cyclic voltammetry of nickel-sulfur complex 1 in trifluoroacetic acid (TFA) in example 1 of the present invention.
FIG. 4 is a graph of electrochemical cyclic voltammetry of nickel-sulfur complex 1 under acetic acid (HOAc) conditions in example 1 of the present invention.
FIG. 5 is a graph showing TOF of nickel-sulfur complex 1 as a function of trifluoroacetic acid concentration ([ TFA ]) in example 1 of the present invention.
FIG. 6 is a graph showing TOF of nickel-sulfur complex 1 in accordance with the concentration of acetic acid ([ HOAc ]) in example 1 of the present invention.
FIG. 7 is a NMR chart of Ni-S complex 2 in example 2 of the present invention.
FIG. 8 is the NMR phosphorus spectrum of the nickel-sulfur complex 2 in example 2 of the present invention.
FIG. 9 is a graph of electrochemical cyclic voltammetry of nickel-sulfur complex 2 under trifluoroacetic acid (TFA) in example 2 of the present invention.
FIG. 10 is a graph of electrochemical cyclic voltammetry of nickel sulfur complex 2 under acetic acid (HOAc) in example 2 of the present invention.
FIG. 11 is a graph showing TOF of nickel-sulfur complex 2 as a function of trifluoroacetic acid concentration ([ TFA ]) in example 2 of the present invention.
FIG. 12 is a graph showing TOF of nickel-sulfur complex 2 as a function of acetic acid concentration ([ HOAc ]) in example 2 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be described in detail below. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the examples given herein without any inventive step, are within the scope of the present invention.
In general, mimetics of the present invention can be prepared by the methods described herein. The following reaction schemes and examples serve to further illustrate the context of the invention.
Those skilled in the art will recognize that: the chemical reactions described herein may be used to suitably prepare other mimetics of the present invention, and other methods for preparing mimetics of the present invention are considered to be within the scope of the present invention. For example, the synthesis of such non-exemplified mimetics according to the present invention can be successfully accomplished by those skilled in the art by modification, such as by the use of other known reagents in addition to those described herein, or by some conventional modification of reaction conditions. In addition, the reactions disclosed herein or known reaction conditions are also recognized as being applicable to the preparation of other mimetics of the same type.
Those skilled in the art will also recognize that: the characteristics of the individual mimetics demonstrated in examples 1 and 2 of the invention (test methods for the catalytic performance of the target nickel- sulfur complexes 1 and 2, test results), as well as other non-exemplified mimetics of the invention, also have a significant catalytic effect in catalyzing the reduction of protonic acid to hydrogen. The mimetics of the present invention (including the exemplified and non-exemplified target mimetics) are merely changes or substitutions to the target mimetics of the examples, and do not significantly adversely affect their effectiveness in catalyzing the reduction of protonic acid to hydrogen.
In the examples listed in the present invention, the chemicals used (i.e., the chemicals listed in the table below) were measured in grams.
Figure BDA0002367211360000051
Example 1
A preparation method of a nickel-sulfur complex 1 containing PCNCP diphosphine ligand is disclosed, and the chemical formula is { (Ph) 2 PCH 2 ) 2 NCH 2 C 6 H 5 }Ni(SCH 2 CH 2 S), the preparation process is as follows:
Figure BDA0002367211360000052
the preparation method comprises the following specific steps:
to a three-necked flask equipped with a stirring magneton was added 1.357g (4.8mmol) [ Ph ] 2 P(CH 2 OH) 2 ] + Cl - 1.67mL (12mmol) of triethylamine and 45mL of a mixed solvent of water and ethanol in a volume ratio of 2:1 to obtain a milky solution, and adding 0.22mL (2.0mmol) of NH into the reaction system 2 CH 2 C 6 H 5 . Heating and refluxing the reaction system at 79 ℃ for 3h, extracting the reaction liquid for 3 times by using dichloromethane, collecting an organic phase, drying the organic phase for 1h by using anhydrous magnesium sulfate, carrying out reduced pressure rotary evaporation to remove the dichloromethane to obtain a light yellow liquid, dissolving the light yellow liquid by using dichloromethane, carrying out preparative silica gel G thin layer chromatography by using a developing agent with the volume ratio of petroleum ether to ethyl acetate of 20:1, collecting a main color band, and obtaining the PCNCP diphosphine ligand (Ph) containing benzyl 2 PCH 2 ) 2 NCH 2 C 6 H 5 The yield thereof was found to be 85%. At room temperature, packagingA single neck flask with stirring magneton was charged with 0.166g (0.70mmol) NiCl 2 ·6H 2 O and 10mL of ethanol solvent to give a green solution, and 0.423g (0.84mmol) of (Ph) was dissolved in 5mL of dichloromethane 2 PCH 2 ) 2 NCH 2 C 6 H 5 Then dropwise adding the mixture into a reaction system, reacting for 5min until a golden yellow solid is generated in a bottle, guiding out the supernatant by using a steel pipe, and washing for 3 times by using diethyl ether to obtain the nickel-chlorine complex { (Ph) containing the PCNCP ligand 2 PCH 2 ) 2 NCH 2 C 6 H 5 }NiCl 2 The yield thereof was found to be 80%. To a flask equipped with a stirring magneton, 0.184g (0.29mmol) { (Ph) was added at room temperature 2 PCH 2 ) 2 NCH 2 C 6 H 5 }NiCl 2 0.02mL (0.24mmol) of ethanedithiol and 15mL of dichloromethane solvent gave a dark green solution, and 0.07mL (0.48mmol) of triethylamine was added to the reaction system. After stirring and reacting for 1h at room temperature, carrying out reduced pressure rotary evaporation to remove dichloromethane, extracting residues with dichloromethane, then carrying out preparative silica gel G thin-layer chromatography separation with a developing agent with a dichloromethane/ethyl acetate volume ratio of 15:1, and collecting a main color band to obtain the nickel-sulfur complex 1 containing the PCNCP diphosphine ligand with the yield of 65%.
The structural characterization data for nickel-sulfur complex 1 are as follows: 1 H NMR(600MHz,CDCl 3 ,TMS):δ7.63(dd,J PH ＝11.4Hz,J HH ＝6.6Hz,8H,2×P(C 6 H 5 -ο) 2 ),7.37(t,J HH ＝7.2Hz,4H,2×P(C 6 H 5 -p) 2 ),7.27(t,J HH ＝7.2Hz,8H,2×P(C 6 H 5 -m) 2 ),7.23(t,J HH ＝7.2Hz,3H,NCH 2 (C 6 H 5 -o,p) 2 ),6.97(d,J HH ＝7.2Hz,2H,NCH 2 (C 6 H 5 -m) 2 ),3.60(s,2H,NCH 2 C 6 H 5 ),3.30(s,4H,2×PCH 2 N),2.73(s,4H,2×SCH 2 )ppm. 31 P{ 1 H}NMR(243MHz,CDCl 3 ,85％H 3 PO 4 ):δ9.05(s)ppm.
FIGS. 1 and 2 show NMR spectra and phosphorus spectra of nickel-sulfur complex 1, in combination with the above data: the nickel-sulfur complex 1 with very high purity can be successfully synthesized by the preparation method.
Electrochemical cyclic voltammetry experiments of nickel sulphur complex 1:
in the experiment, a glassy carbon electrode with the diameter of 3mm is used as a working electrode, a platinum wire is used as a counter electrode, and non-aqueous Ag/AgNO is used on a CHI 660E electrochemical instrument 3 (0.01M AgNO 3 /0.1M n-Bu 4 NPF 6 /CH 3 CN) is a classical three-electrode system of a reference electrode, and the measurement is carried out in a cylindrical groove and under the nitrogen atmosphere; before each test, 0.05 mu m of aluminum oxide powder is used for polishing a glassy carbon electrode, then ultrasonic cleaning is carried out in water, finally acetone washing and cold air blow-drying are carried out; the solvent of the test system is chromatographic pure acetonitrile, the nickel-sulfur complex 1 is 1mmol/L, and the supporting electrolyte is n-Bu with the concentration of 0.1mol/L 4 NPF 6 The protonic acid is trifluoroacetic acid or acetic acid of 0, 2, 4, 6, 8, 10mmol/L, and the scanning rate is 100mV s -1 The potentials obtained by the test are all ferrocene-corrected reduction potentials. Meanwhile, according to a calculation formula k of catalytic efficiency TOF of hydrogen evolution reaction obs (TOF)＝1.94ν(i cat /i p ) 2 And obtaining the TOF value of the theoretical catalytic efficiency.
FIGS. 3 and 4 are graphs of electrochemical cyclic voltammetry of nickel-sulfur complex 1 in the presence of trifluoroacetic acid or acetic acid, respectively, and the results show that: the nickel-sulfur complex 1 has the function of electrocatalysis of proton reduction to hydrogen under the condition of strong acid or weak acid.
FIGS. 5 and 6 are graphs of TOF of nickel-sulfur complex 1 as a function of trifluoroacetic acid or acetic acid concentration, respectively, and the results show that: the theoretical catalytic efficiency TOF of the nickel-sulfur complex 1 increases linearly with increasing concentration of trifluoroacetic acid or acetic acid, and is respectively 11.35s when 10mM of trifluoroacetic acid or acetic acid is taken as protonic acid -1 And 2.37s -1 。
Example 2
A preparation method of a nickel-sulfur complex 2 containing PCNCP diphosphine ligand is disclosed, and the chemical formula is { (Ph) 2 PCH 2 ) 2 NCH 2 C 5 H 4 N}Ni(SCH 2 CH 2 S), the preparation process is as follows:
Figure BDA0002367211360000071
the specific synthesis steps are as follows:
to a three-necked flask equipped with a stirring magneton was added 1.357g (4.8mmol) [ Ph ] 2 P(CH 2 OH) 2 ] + Cl - 1.67mL (12mmol) of triethylamine and 45mL of a solvent with a volume ratio of water to ethanol of 2:1 to obtain a milky solution, and 0.20mL (2.0mmol) of NH was added to the reaction system 2 CH 2 C 5 H 4 And N is added. Heating and refluxing at 79 deg.C for 3 hr, extracting with dichloromethane for 3 times, collecting organic phase, drying with anhydrous magnesium sulfate for 1 hr, rotary evaporating under reduced pressure to remove dichloromethane to obtain light yellow liquid, extracting with dichloromethane, separating with neutral alumina column chromatography with dichloromethane/ethyl acetate at volume ratio of 1:1, collecting main color band to obtain PCNCP diphosphine ligand (Ph) 2 PCH 2 ) 2 NCH 2 C 5 H 4 N, yield 88%. 0.166g (0.70mmol) NiCl was added to a flask equipped with a stirring magneton at room temperature 2 ·6H 2 O and 10mL of ethanol solvent to give a green solution, and 0.477g (0.95mmol) of (Ph) was dissolved in 5mL of dichloromethane 2 PCH 2 ) 2 NCH 2 C 5 H 4 Dropwise adding the solution into a reaction system after N, reacting for 5min until black solid is generated in the bottle, guiding out the supernatant by using a steel pipe, and washing with diethyl ether for 3 times to obtain the nickel-chlorine complex { (Ph) containing PCNCP ligand 2 PCH 2 ) 2 NCH 2 C 5 H 4 N}NiCl 2 The yield thereof was found to be 76%. To a flask equipped with a stirring magneton, 0.229g (0.36mmol) { (Ph) was added at room temperature 2 PCH 2 ) 2 NCH 2 C 5 H 4 N}NiCl 2 0.02mL (0.24mmol) of ethanedithiolAnd 15mL of a methylene chloride solvent to obtain a black-green solution, and 0.07mL (0.48mmol) of triethylamine was added to the reaction system. After stirring and reacting for 1h at room temperature, carrying out reduced pressure rotary evaporation to remove dichloromethane, extracting residues with dichloromethane, then carrying out preparative silica gel G thin layer chromatography separation with a developing agent with a dichloromethane/ethyl acetate volume ratio of 1:1, and collecting a main color band to obtain the nickel-sulfur complex 2 containing the PCNCP diphosphine ligand with the yield of 86%.
The structural characterization data for nickel-sulfur complex 2 are as follows: 1 H NMR(600MHz,CDCl 3 ,TMS):δ8.39(d,J HH ＝4.2Hz,2H,C 5 H 4 N),7.68(q,J HH ＝6.0Hz,8H,2xP(C 6 H 5 -ο) 2 ),7.41(t,J HH ＝7.8Hz,4H,2xP(C 6 H 5 -p) 2 ),7.31(t,J HH ＝7.8Hz,8H,2xP(C 6 H 5 -m) 2 ),6.78(d,J HH ＝4.2Hz,2H,C 5 H 4 N),3.58(s,2H,NCH 2 C 5 H 4 N),3.31(s,4H,2xPCH 2 N),2.73(s,4H,2xSCH 2 )ppm. 31 P{ 1 H}NMR(243MHz,CDCl 3 ,85％H 3 PO 4 ):δ9.40(s)ppm.
FIGS. 7 and 8 are NMR hydrogen and phosphorus spectra of nickel-sulfur complex 2, taken in conjunction with the above data, showing that: the preparation method of the invention can successfully synthesize the nickel-sulfur complex 2 with very high purity.
Electrochemical cyclic voltammetry experiment of nickel sulphur complex 2:
in the experiment, a glassy carbon electrode with the diameter of 3mm is used as a working electrode, a platinum wire is used as a counter electrode, and non-aqueous Ag/AgNO is used on a CHI 660E electrochemical instrument 3 (0.01M AgNO 3 /0.1M n-Bu 4 NPF 6 /CH 3 CN) is a classical three-electrode system of a reference electrode, and the measurement is carried out in a cylindrical groove and under the nitrogen atmosphere; before each test, 0.05 mu m of aluminum oxide powder is used for polishing a glassy carbon electrode, then ultrasonic cleaning is carried out in water, finally acetone washing and cold air blow-drying are carried out; the solvent of the test system is chromatographic pure acetonitrile, the nickel-sulfur complex 2 is 1mmol/L, and the supporting electrolyte is n-Bu with the concentration of 0.1mol/L 4 NPF 6 The protonic acid is trifluoroacetic acid or acetic acid of 0, 2, 4, 6, 8, 10mmol/L and the scanning rate is 100mV s -1 The potentials obtained by the test are all ferrocene-corrected reduction potentials. Meanwhile, according to a calculation formula k of catalytic efficiency TOF of hydrogen evolution reaction obs (TOF)＝1.94ν(i cat /i p ) 2 And obtaining the TOF value of the theoretical catalytic efficiency.
FIGS. 9 and 10 are graphs of electrochemical cyclic voltammetry of nickel-sulfur complex 2 in the presence of trifluoroacetic acid or acetic acid, respectively, and the results show that: the nickel-sulfur complex 2 has the function of electrocatalysis of proton reduction to hydrogen under the condition of strong acid or weak acid.
FIGS. 11 and 12 are graphs of TOF of nickel-sulfur complex 2 as a function of trifluoroacetic acid or acetic acid concentration, respectively, showing that: the theoretical catalytic efficiency TOF of the nickel-sulfur complex 2 increases linearly with increasing concentration of trifluoroacetic acid or acetic acid, and is 4.25s when 10mM of trifluoroacetic acid or acetic acid is used as protonic acid -1 And 2.15s -1 。
The above description is only for the specific embodiments of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can easily think of the changes or substitutions within the technical scope of the present invention, and shall cover the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the appended claims.

Claims (1)

1. The application of the nickel-sulfur complex containing the PCNCP diphosphine ligand in electrocatalytic trifluoroacetic acid reduction to hydrogen is disclosed, and the molecular structural formula of the nickel-sulfur complex containing the PCNCP diphosphine ligand is shown as follows:
Figure DEST_PATH_IMAGE001
；
wherein R is benzyl CH 2 C 6 H 5 。
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CN108484685A (en) * 2018-03-22 2018-09-04 四川理工学院 A kind of application of Mononuclear nickel complex as electro-catalysis hydrogen manufacturing and photocatalytically degradating organic dye catalyst
CN108912179A (en) * 2018-06-27 2018-11-30 四川理工学院 A kind of application of the Mononuclear nickel complex of the ligand containing mnt as electro-catalysis catalyst for preparing hydrogen
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